Ethylene/alpha-olefins block interpolymers

ABSTRACT

Embodiments of the invention provide a class of ethylene/α-olefin block interpolymers. The ethylene/α-olefin interpolymers are characterized by an average block index, ABI, which is greater than zero and up to about 1.0 and a molecular weight distribution, M w /M n , greater than about 1.3. Preferably, the block index is from about 0.2 to about 1. In addition or alternatively, the block ethylene/α-olefin interpolymer is characterized by having at least one fraction obtained by Temperature Rising Elution Fractionation (“TREF”), wherein the fraction has a block index greater than about 0.3 and up to about 1.0 and the ethylene/α-olefin interpolymer has a molecular weight distribution, M w /M n , greater than about 1.3.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims priority to PCT Application No.PCT/US2005/008917, filed on Mar. 17, 2005, which in turn claims priorityto U.S. Provisional Application No. 60/553,906, filed Mar. 17, 2004; theapplication further claims priority to U.S. Provisional Application Ser.No. 60/717,822, filed Sep. 16, 2005. For purposes of United Statespatent practice, the contents of the provisional application and the PCTapplication are herein incorporated by reference in their entirety.

FIELD OF THE INVENTION

This invention relates to ethylene/α-olefin block interpolymers andproducts made from the block interpolymers.

BACKGROUND OF THE INVENTION

Block copolymers comprise sequences (“blocks”), of the same monomerunit, covalently bound to sequences of unlike type. The blocks can beconnected in a variety of ways, such as A-B in diblock and A-B-Atriblock structures, where A represents one block and B represents adifferent block. In a multi-block copolymer, A and B can be connected ina number of different ways and be repeated multiply. It may furthercomprise additional blocks of different type. Multi-block copolymers canbe either linear multi-block or multi-block star polymers (in which allblocks bond to the same atom or chemical moiety).

A block copolymer is created when two or more polymer molecules ofdifferent chemical composition are covalently bonded in an end-to-endfashion. While a wide variety of block copolymer architectures arepossible, most block copolymers involve the covalent bonding of hardplastic blocks, which are substantially crystalline or glassy, toelastomeric blocks forming thermoplastic elastomers. Other blockcopolymers, such as rubber-rubber (elastomer-elastomer), glass-glass,and glass-crystalline block copolymers, are also possible and may havecommercial importance.

One method to make block copolymers is to produce a “living polymer”.Unlike typical Ziegler-Natta polymerization processes, livingpolymerization processes involve only initiation and propagation stepsand essentially lack chain terminating side reactions. This permits thesynthesis of predetermined and well-controlled structures desired in ablock copolymer. A polymer created in a “living” system can have anarrow or extremely narrow distribution of molecular weight and beessentially monodisperse (i.e., the molecular weight distribution isessentially one). Living catalyst systems are characterized by aninitiation rate which is on the order of or exceeds the propagationrate, and the absence of termination or transfer reactions. In addition,these catalyst systems are characterized by the presence of a singletype of active site. To produce a high yield of block copolymer in apolymerization process, the catalyst must exhibit living characteristicsto a substantial extent.

Butadiene-isoprene block copolymers have been synthesized via anionicpolymerization using the sequential monomer addition technique. Insequential addition, a certain amount of one of the monomers iscontacted with the catalyst. Once a first such monomer has reacted tosubstantial extinction forming the first block, a certain amount of thesecond monomer or monomer species is introduced and allowed to react toform the second block. The process may be repeated using the same orother anionically polymerizable monomers. However, ethylene and otherα-olefins, such as propylene, butene, 1-octene, etc., are not directlyblock polymerizable by anionic techniques.

Therefore, there is an unfulfilled need for block copolymers which arebased on ethylene and α-olefins. There is also a need for a method ofmaking such block copolymers.

SUMMARY OF THE INVENTION

The aforementioned needs are met by various aspects of the invention. Inone aspect, the invention relates to an ethylene/α-olefin interpolymercomprising polymerized units of ethylene and α-olefin, wherein theinterpolymer is characterized by an average block index greater thanzero and up to about 1.0 and a molecular weight distribution,M_(w)/M_(n), greater than about 1.3. In another aspect, the inventionrelates to an ethylene/α-olefin interpolymer comprising polymerizedunits of ethylene and α-olefin, wherein the average block index isgreater than 0 but less than about 0.4 and a molecular weightdistribution, M_(w)/M_(n), greater than about 1.3. Preferably, theinterpolymer is a linear, multi-block copolymer with at least threeblocks. Also preferably, the ethylene content in the interpolymer is atleast 50 mole percent.

In some embodiments, the average block index of the interpolymer is inthe range from about 0.1 to about 0.3, from about 0.4 to about 1.0, fromabout 0.3 to about 0.7, from about 0.6 to about 0.9, or from about 0.5to about 0.7. In other embodiments, the interpolymer has a density ofless than about 0.91 g/cc, such as from about 0.86 g/cc to about 0.91g/cc. In some embodiments, the α-olefin in the ethylene/α-olefininterpolymer is styrene, propylene, 1-butene, 1-hexene, 1-octene,4-methyl-1-pentene, norbornene, 1-decene, 1,5-hexadiene, or acombination thereof. In other embodiments, the molecular weightdistribution, M_(w)/M_(n), is greater than about 1.5 or greater thanabout 2.0. It can also range from about 2.0 to about 8 or from about 1.7to about 3.5.

In yet another aspect, the invention relates to an ethylene/α-olefininterpolymer comprising polymerized units of ethylene and α-olefin, theinterpolymer characterized by having at least one fraction obtained byTemperature Rising Elution Fractionation (“TREF”), wherein the fractionhas a block index greater than about 0.3 and up to about 1.0 and theethylene/α-olefin interpolymer has a molecular weight distribution,M_(w)/M_(n), greater than about 1.3. In still another aspect, theinvention relates to an ethylene/α-olefin interpolymer comprisingpolymerized units of ethylene and α-olefin, the interpolymercharacterized by having at least one fraction obtained by TREF, whereinthe fraction has a block index greater than about 0 and up to about 0.4and the ethylene/α-olefin interpolymer has a molecular weightdistribution, M_(w)/M_(n), greater than about 1.3. In some embodiments,the block index of the fraction is greater than about 0.4, greater thanabout 0.5, greater than about 0.6, greater than about 0.7, greater thanabout 0.8, or greater than about 0.9.

The interpolymer comprises one or more hard segments and one or moresoft segments. Preferably, the hard segments comprise at least 98% ofethylene by weight, and the soft segments comprise less than 95%,preferably less than 50%, of ethylene by weight. In some embodiments,the hard segments are present in an amount from about 5% to about 85% byweight of the interpolymer. In other embodiments, the interpolymercomprises at least 5 or at least 10 hard and soft segments connected ina linear fashion to form a linear chain. Preferably, the hard segmentsand soft segments are randomly distributed along the chain. In someembodiments, neither the soft segments nor the hard segments include atip segment (which is different by chemical composition than the rest ofthe segments).

Methods of making the interpolymers are also provided herein. Additionalaspects of the invention and characteristics and properties of variousembodiments of the invention become apparent with the followingdescription.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows the melting point/density relationship for the inventivepolymers (represented by diamonds) as compared to traditional randomcopolymers (represented by circles) and Ziegler-Natta copolymers(represented by triangles).

FIG. 2 shows plots of delta DSC-CRYSTAF as a function of DSC MeltEnthalpy for various polymers. The diamonds represent randomethylene/octene copolymers; the squares represent polymer examples 1-4;the triangles represent polymer examples 5-9; and the circles representpolymer examples 10-19. The “X” symbols represent polymer examplesA*-F*.

FIG. 3 shows the effect of density on elastic recovery for unorientedfilms made from inventive interpolymers (represented by the squares andcircles) and traditional copolymers (represented by the triangles whichare Dow AFFINITY® polymers). The squares represent inventiveethylene/butene copolymers; and the circles represent inventiveethylene/octene copolymers.

FIG. 4 is a plot of octene content of Temperature Rising ElutionFractionation (“TREF”) fractionated ethylene/1-octene copolymerfractions versus TREF elution temperature of the fraction for thepolymer of Example 5 (represented by the circles) and comparativepolymers E and F (represented by the “X” symbols). The diamondsrepresent traditional random ethylene/octene copolymers.

FIG. 5 is a plot of octene content of TREF fractionatedethylene/1-octene copolymer fractions versus ATREF elution temperatureof the fraction for the polymer of Example 5 and for comparative F*. Thesquares represent Polymer Example F*; and the triangles representPolymer Example 5. Also shown is the ATREF temperature distribution forExample 5 (curve 1) and comparative F* (curve 2).

FIG. 6 is a graph of log storage modulus as a function of temperaturefor comparative ethylene/1-octene copolymer (curve 2) andpropylene/ethylene copolymer (curve 3) and for two ethylene/1-octeneblock copolymers according to embodiments of the invention made withdiffering quantities of chain shuttling agent (curves 1).

FIG. 7 shows a plot of Thermomechanical Analysis (“TMA”) (1 mm) versusflex modulus for some inventive polymers (represented by the diamonds),as compared to some known polymers. The triangles represent Dow VERSIFY®polymers; the circles represent random ethylene/styrene copolymers; andthe squares represent Dow AFFINITY® polymers.

FIG. 8 is plot of natural log ethylene mole fraction for randomethylene/α-olefin copolymers as a function of the inverse of DSC peakmelting temperature or ATREF peak temperature. The filled squaresrepresent data points obtained from random homogeneously branchedethylene/α-olefin copolymers in ATREF; and the open squares representdata points obtained from random homogeneously branchedethylene/α-olefin copolymers in DSC. “P” is the ethylene mole fraction;“T” is the temperature in Kelvin.

FIG. 9 is a plot constructed on the basis of the Flory equation forrandom ethylene/α-olefin copolymers to illustrate the definition of“block index.” “A” represents the whole, perfect random copolymer; “B”represents a pure “hard segment”; and “C” represents the whole, perfectblock copolymer having the same comonomer content as “A”. A, B, and Cdefine a triangular area within which most TREF fractions would fall.

FIG. 10 is a plot of the block index calculated for each TREF fractionfor four polymers. The diamond represent Polymer F* with an averageblock index of 0; the triangles represent Polymer 5 with an averageblock index of 0.53; the squares represent Polymer 8 with an averageblock index of 0.59; and the “X” represents Polymer 20 with an averageblock index of 0.20.

FIG. 11 is a plot of the block index calculated for each TREF fractionfor two inventive polymers: the filled bars represent Polymer 18B; andthe open bars represent Polymer 5.

FIG. 12 is a plot of the average block index calculated for ninedifferent polymers as a function of the diethyl zinc concentrationduring polymerization in terms of “[Zn/C₂H₄]*1000.” “x” represents aninventive ethylene/propylene block copolymer (Polymer 23); the twotriangles represent two inventive ethylene/butene block copolymers(Polymer 21 and Polymer 22); and the squares represent ethylene/octenecopolymers made at different levels of diethyl zinc (including one madewithout any diethyl zinc).

FIG. 13 is a plot of the square root of the second moment about the meanweight average block index as a function of [Zn/C₂H₄]*1000.

FIG. 14 is a representation of a normal DSC profile for an inventivepolymer.

FIG. 15 is a weighted DSC profile obtained by converting FIG. 14.

FIG. 16 is a ¹³C NMR spectrum of Polymer 19A.

DESCRIPTION OF EMBODIMENTS OF THE INVENTION General Definitions

“Polymer” means a polymeric compound prepared by polymerizing monomers,whether of the same or a different type. The generic term “polymer”embraces the terms “homopolymer,” “copolymer,” “terpolymer” as well as“interpolymer.”

“Interpolymer” means a polymer prepared by the polymerization of atleast two different types of monomers. The generic term “interpolymer”includes the term “copolymer” (which is usually employed to refer to apolymer prepared from two different monomers) as well as the term“terpolymer” (which is usually employed to refer to a polymer preparedfrom three different types of monomers). It also encompasses polymersmade by polymerizing four or more types of monomers.

The term “ethylene/α-olefin interpolymer” generally refers to polymerscomprising ethylene and an α-olefin having 3 or more carbon atoms.Preferably, ethylene comprises the majority mole fraction of the wholepolymer, i.e., ethylene comprises at least about 50 mole percent of thewhole polymer. More preferably ethylene comprises at least about 60 molepercent, at least about 70 mole percent, or at least about 80 molepercent, with the substantial remainder of the whole polymer comprisingat least one other comonomer that is preferably an α-olefin having 3 ormore carbon atoms. For many ethylene/octene copolymers, the preferredcomposition comprises an ethylene content greater than about 80 molepercent of the whole polymer and an octene content of from about 10 toabout 15, preferably from about 15 to about 20 mole percent of the wholepolymer. In some embodiments, the ethylene/α-olefin interpolymers do notinclude those produced in low yields or in a minor amount or as aby-product of a chemical process. While the ethylene/α-olefininterpolymers can be blended with one or more polymers, the as-producedethylene/α-olefin interpolymers are substantially pure and oftencomprise a major component of the reaction product of a polymerizationprocess.

The term “crystalline” if employed, refers to a polymer or a segmentthat possesses a first order transition or crystalline melting point(Tm) as determined by differential scanning calorimetry (DSC) orequivalent technique. The term may be used interchangeably with the term“semicrystalline”. The term “amorphous” refers to a polymer lacking acrystalline melting point as determined by differential scanningcalorimetry (DSC) or equivalent technique.

The term “multi-block copolymer” or “segmented copolymer” refers to apolymer comprising two or more chemically distinct regions or segments(also referred to as “blocks”) preferably joined in a linear manner,that is, a polymer comprising chemically differentiated units which arejoined end-to-end with respect to polymerized ethylenic functionality,rather than in pendent or grafted fashion. In a preferred embodiment,the blocks differ in the amount or type of comonomer incorporatedtherein, the density, the amount of crystallinity, the crystallite sizeattributable to a polymer of such composition, the type or degree oftacticity (isotactic or syndiotactic), regio-regularity orregio-irregularity, the amount of branching, including long chainbranching or hyper-branching, the homogeneity, or any other chemical orphysical property. The multi-block copolymers are characterized byunique distributions of both polydispersity index (PD₁ or M_(w)/M_(n)),block length distribution, and/or block number distribution due to theunique process making of the copolymers. More specifically, whenproduced in a continuous process, the polymers desirably possess PDIfrom about 1.7 to about 8, preferably from about 1.7 to about 3.5, morepreferably from about 1.7 to about 2.5, and most preferably from about1.8 to about 2.5 or from about 1.8 to about 2.1. When produced in abatch or semi-batch process, the polymers possess PDI from about 1.0 toabout 2.9, preferably from about 1.3 to about 2.5, more preferably fromabout 1.4 to about 2.0, and most preferably from about 1.4 to about 1.8.It is noted that “block(s)” and “segment(s)” are used hereininterchangeably.

In the following description, all numbers disclosed herein areapproximate values, regardless whether the word “about” or “approximate”is used in connection therewith. They may vary by 1 percent, 2 percent,5 percent, or, sometimes, 10 to 20 percent. Whenever a numerical rangewith a lower limit, R^(L) and an upper limit, R^(U), is disclosed, anynumber falling within the range is specifically disclosed. Inparticular, the following numbers within the range are specificallydisclosed: R=R^(L)+k*(R^(U)−R^(L)), wherein k is a variable ranging from1 percent to 100 percent with a 1 percent increment, i.e., k is 1percent, 2 percent, 3 percent, 4 percent, 5 percent, . . . , 50 percent,51 percent, 52 percent, . . . , 95 percent, 96 percent, 97 percent, 98percent, 99 percent, or 100 percent. Moreover, any numerical rangedefined by two R numbers as defined in the above is also specificallydisclosed.

Embodiments of the invention provide a new class of ethylene/α-olefinblock interpolymers (hereinafter “inventive polymer”, “ethylene/α-olefininterpolymers”, or variations thereof). The ethylene/α-olefininterpolymers comprise ethylene and one or more copolymerizable α-olefincomonomers in polymerized form, characterized by multiple blocks orsegments of two or more polymerized monomer units differing in chemicalor physical properties. That is, the ethylene/α-olefin interpolymers areblock interpolymers, preferably multi-block interpolymers or copolymers.The terms “interpolymer” and copolymer” are used interchangeably herein.In some embodiments, the multi-block copolymer can be represented by thefollowing formula:

(AB)_(n)

where n is at least 1, preferably an integer greater than 1, such as 2,3, 4, 5, 10, 15, 20, 30, 40, 50, 60, 70, 80, 90, 100, or higher, “A”represents a hard block or segment and “B” represents a soft block orsegment. Preferably, As and Bs are linked in a linear fashion, not in abranched or a star fashion. “Hard” segments refer to blocks ofpolymerized units in which ethylene is present in an amount greater than95 weight percent, and preferably greater than 98 weight percent. Inother words, the comonomer content in the hard segments is less than 5weight percent, and preferably less than 2 weight percent. In someembodiments, the hard segments comprises all or substantially allethylene. “Soft” segments, on the other hand, refer to blocks ofpolymerized units in which the comonomer content is greater than 5weight percent, preferably greater than 8 weight percent, greater than10 weight percent, or greater than 15 weight percent. In someembodiments, the comonomer content in the soft segments can be greaterthan 20 weight percent, greater than 25 eight percent, greater than 30weight percent, greater than 35 weight percent, greater than 40 weightpercent, greater than 45 weight percent, greater than 50 weight percent,or greater than 60 weight percent.

In some embodiments, A blocks and B blocks are randomly distributedalong the polymer chain. In other words, the block copolymers usually donot have a structure like:

AAA-AA-BBB-BB

In other embodiments, the block copolymers usually do not have a thirdtype of block. In still other embodiments, each of block A and block Bhas monomers or comonomers randomly distributed within the block. Inother words, neither block A nor block B comprises two or more segments(or sub-blocks) of distinct composition, such as a tip segment, whichhas a different composition than the rest of the block.

The ethylene/α-olefin interpolymers are characterized by an averageblock index, ABI, which is greater than zero and up to about 1.0 and amolecular weight distribution, M_(w)/M_(n), greater than about 1.3. Theaverage block index, ABI, is the weight average of the block index(“BI”) for each of the polymer fractions obtained in preparative TREF(i.e., fractionation of a polymer by Temperature Rising ElutionFractionation) from 20° C. and 110° C., with an increment of 5° C.(although other temperature increments, such as 1° C., 2° C., 10° C.,also can be used):

ABI=Σ(w _(i) BI _(i))

where BI_(i) is the block index for the ith fraction of the inventiveethylene/α-olefin interpolymer obtained in preparative TREF, and w_(i)is the weight percentage of the ith fraction. Similarly, the square rootof the second moment about the mean, hereinafter referred to as thesecond moment weight average block index, can be defined as follows.

${2^{nd}\mspace{14mu} {moment}\mspace{14mu} {weight}{\mspace{11mu} \;}{average}\mspace{14mu} B\; I} = \sqrt{\frac{\sum\left( {w_{i}\left( {{BI}_{i} - {ABI}} \right)}^{2} \right)}{\frac{\left( {N - 1} \right){\sum w_{i}}}{N}}}$

where N is defined as the number of fractions with BI_(i) greater thanzero. Referring to FIG. 9, for each polymer fraction, BI is defined byone of the two following equations (both of which give the same BIvalue):

${B\; I} = {{\frac{{1/T_{X}} - {1/T_{XO}}}{{1/T_{A}} - {1/T_{AB}}}\mspace{14mu} {or}\mspace{14mu} B\; I} = {- \frac{{{Ln}\; P_{X}} - {{Ln}\; P_{XO}}}{{{Ln}\; P_{A}} - {{Ln}\; P_{AB}}}}}$

where T_(X) is the ATREF (i.e., analytical TREF) elution temperature forthe ith fraction (preferably expressed in Kelvin), P_(x) is the ethylenemole fraction for the ith fraction, which can be measured by NMR or IRas described below. P_(AB) is the ethylene mole fraction of the wholeethylene/α-olefin interpolymer (before fractionation), which also can bemeasured by NMR or IR. T_(A) and P_(A) are the ATREF elution temperatureand the ethylene mole fraction for pure “hard segments” (which refer tothe crystalline segments of the interpolymer). As an approximation orfor polymers where the “hard segment” composition is unknown, the T_(A)and P_(A) values are set to those for high density polyethylenehomopolymer.

T_(AB) is the ATREF elution temperature for a random copolymer of thesame composition (having an ethylene mole fraction of P_(AB)) andmolecular weight as the inventive copolymer. T_(AB) can be calculatedfrom the mole fraction of ethylene (measured by NMR) using the followingequation:

LnP _(AB)=α/T_(AB)+β

where α and β are two constants which can be determined by a calibrationusing a number of well characterized preparative TREF fractions of abroad composition random copolymer and/or well characterized randomethylene copolymers with narrow composition. It should be noted that αand β may vary from instrument to instrument. Moreover, one would needto create an appropriate calibration curve with the polymer compositionof interest, using appropriate molecular weight ranges and comonomertype for the preparative TREF fractions and/or random copolymers used tocreate the calibration. There is a slight molecular weight effect. Ifthe calibration curve is obtained from similar molecular weight ranges,such effect would be essentially negligible. In some embodiments asillustrated in FIG. 8, random ethylene copolymers and/or preparativeTREF fractions of random copolymers satisfy the following relationship:

LnP=−237.83/T _(ATREF)+0.639

The above calibration equation relates the mole fraction of ethylene, P,to the analytical TREF elution temperature, T_(ATREF), for narrowcomposition random copolymers and/or preparative TREF fractions of broadcomposition random copolymers. T_(XO) is the ATREF temperature for arandom copolymer of the same composition (i.e., the same comonomer typeand content) and the same molecular weight and having an ethylene molefraction of P_(X). T_(XO) can be calculated from LnP_(X)=α/T_(XO)+β froma measured P_(X) mole fraction. Conversely, P_(XO) is the ethylene molefraction for a random copolymer of the same composition (i.e., the samecomonomer type and content) and the same molecular weight and having anATREF temperature of T_(x), which can be calculated from LnP_(XO)=α/T_(X)+β using a measured value of T_(X).

Once the block index (BI) for each preparative TREF fraction isobtained, the weight average block index, ABI, for the whole polymer canbe calculated. In some embodiments, ABI is greater than zero but lessthan about 0.4 or from about 0.1 to about 0.3. In other embodiments, ABIis greater than about 0.4 and up to about 1.0. Preferably, ABI should bein the range of from about 0.4 to about 0.7, from about 0.5 to about0.7, or from about 0.6 to about 0.9. In some embodiments, ABI is in therange of from about 0.3 to about 0.9, from about 0.3 to about 0.8, orfrom about 0.3 to about 0.7, from about 0.3 to about 0.6, from about 0.3to about 0.5, or from about 0.3 to about 0.4. In other embodiments, ABIis in the range of from about 0.4 to about 1.0, from about 0.5 to about1.0, or from about 0.6 to about 1.0, from about 0.7 to about 1.0, fromabout 0.8 to about 1.0, or from about 0.9 to about 1.0.

Another characteristic of the inventive ethylene/α-olefin interpolymeris that the inventive ethylene/α-olefin interpolymer comprises at leastone polymer fraction which can be obtained by preparative TREF, whereinthe fraction has a block index greater than about 0.1 and up to about1.0 and the polymer having a molecular weight distribution, M_(w)/M_(n),greater than about 1.3. In some embodiments, the polymer fraction has ablock index greater than about 0.6 and up to about 1.0, greater thanabout 0.7 and up to about 1.0, greater than about 0.8 and up to about1.0, or greater than about 0.9 and up to about 1.0. In otherembodiments, the polymer fraction has a block index greater than about0.1 and up to about 1.0, greater than about 0.2 and up to about 1.0,greater than about 0.3 and up to about 1.0, greater than about 0.4 andup to about 1.0, or greater than about 0.4 and up to about 1.0. In stillother embodiments, the polymer fraction has a block index greater thanabout 0.1 and up to about 0.5, greater than about 0.2 and up to about0.5, greater than about 0.3 and up to about 0.5, or greater than about0.4 and up to about 0.5. In yet other embodiments, the polymer fractionhas a block index greater than about 0.2 and up to about 0.9, greaterthan about 0.3 and up to about 0.8, greater than about 0.4 and up toabout 0.7, or greater than about 0.5 and up to about 0.6.

In addition to an average block index and individual fraction blockindices, the ethylene/α-olefin interpolymers are characterized by one ormore of the properties described as follows.

In one aspect, the ethylene/α-olefin interpolymers used in embodimentsof the invention have a M_(w)/M_(n) from about 1.7 to about 3.5 and atleast one melting point, T_(m), in degrees Celsius and density, d, ingrams/cubic centimeter, wherein the numerical values of the variablescorrespond to the relationship:

T _(m)>−2002.9+4538.5(d)−2422.2(d)², and preferably

T _(m)≧−6288.1+13141(d)−6720.3(d)², and more preferably

T _(m)≧858.91−1825.3(d)+1112.8(d)².

Such melting point/density relationship is illustrated in FIG. 1. Unlikethe traditional random copolymers of ethylene/α-olefins whose meltingpoints decrease with decreasing densities, the inventive interpolymers(represented by diamonds) exhibit melting points substantiallyindependent of the density, particularly when density is between about0.87 g/cc to about 0.95 g/cc. For example, the melting point of suchpolymers are in the range of about 110° C. to about 130° C. when densityranges from 0.875 g/cc to about 0.945 g/cc. In some embodiments, themelting point of such polymers are in the range of about 115° C. toabout 125° C. when density ranges from 0.875 g/cc to about 0.945 g/cc.

In another aspect, the ethylene/α-olefin interpolymers comprise, inpolymerized form, ethylene and one or more α-olefins and arecharacterized by a ΔT, in degree Celsius, defined as the temperature forthe tallest Differential Scanning Calorimetry (“DSC”) peak minus thetemperature for the tallest Crystallization Analysis Fractionation(“CRYSTAF”) peak and a heat of fusion in J/g, ΔH, and ΔT and ΔH satisfythe following relationships:

ΔT>−0.1299(ΔH)+62.81, and preferably

ΔT≧−0.1299(ΔH)+64.38, and more preferably

ΔT≧−0.1299(ΔH)+65.95,

for ΔH up to 130 J/g. Moreover, ΔT is equal to or greater than 48° C.for ΔH greater than 130 J/g. The CRYSTAF peak is determined using atleast 5 percent of the cumulative polymer (that is, the peak mustrepresent at least 5 percent of the cumulative polymer), and if lessthan 5 percent of the polymer has an identifiable CRYSTAF peak, then theCRYSTAF temperature is 30° C., and ΔH is the numerical value of the heatof fusion in J/g. More preferably, the highest CRYSTAF peak contains atleast 10 percent of the cumulative polymer. FIG. 2 shows plotted datafor inventive polymers as well as comparative examples. Integrated peakareas and peak temperatures are calculated by the computerized drawingprogram supplied by the instrument maker. The diagonal line shown forthe random ethylene octene comparative polymers corresponds to theequation ΔT=−0.1299 (ΔH)+62.81.

In yet another aspect, the ethylene/α-olefin interpolymers have amolecular fraction which elutes between 40° C. and 130° C. whenfractionated using Temperature Rising Elution Fractionation (“TREF”),characterized in that said fraction has a molar comonomer contenthigher, preferably at least 5 percent higher, more preferably at least10 percent higher, than that of a comparable random ethyleneinterpolymer fraction eluting between the same temperatures, wherein thecomparable random ethylene interpolymer contains the same comonomer(s),and has a melt index, density, and molar comonomer content (based on thewhole polymer) within 10 percent of that of the block interpolymer.Preferably, the Mw/Mn of the comparable interpolymer is also within 10percent of that of the block interpolymer and/or the comparableinterpolymer has a total comonomer content within 10 weight percent ofthat of the block interpolymer.

In still another aspect, the ethylene/α-olefin interpolymers arecharacterized by an elastic recovery, Re, in percent at 300 percentstrain and 1 cycle measured on a compression-molded film of anethylene/α-olefin interpolymer, and has a density, d, in grams/cubiccentimeter, wherein the numerical values of Re and d satisfy thefollowing relationship when ethylene/α-olefin interpolymer issubstantially free of a cross-linked phase:

Re>1481−1629(d); and preferably

Re≧1491−1629(d); and more preferably

Re≧1501−1629(d); and even more preferably

Re≧1511−1629(d).

FIG. 3 shows the effect of density on elastic recovery for unorientedfilms made from certain inventive interpolymers and traditional randomcopolymers. For the same density, the inventive interpolymers havesubstantially higher elastic recoveries.

In some embodiments, the ethylene/α-olefin interpolymers have a tensilestrength above 10 MPa, preferably a tensile strength≧11 MPa, morepreferably a tensile strength≧13 MPa and/or an elongation at break of atleast 600 percent, more preferably at least 700 percent, highlypreferably at least 800 percent, and most highly preferably at least 900percent at a crosshead separation rate of 11 cm/minute.

In other embodiments, the ethylene/α-olefin interpolymers have (1) astorage modulus ratio, G'(25° C.)/G'(100° C.), of from 1 to 50,preferably from 1 to 20, more preferably from 1 to 10; and/or (2) a 70°C. compression set of less than 80 percent, preferably less than 70percent, especially less than 60 percent, less than 50 percent, or lessthan 40 percent, down to a compression set of 0 percent.

In still other embodiments, the ethylene/α-olefin interpolymers have a70° C. compression set of less than 80 percent, less than 70 percent,less than 60 percent, or less than 50 percent. Preferably, the 70° C.compression set of the interpolymers is less than 40 percent, less than30 percent, less than 20 percent, and may go down to about 0 percent.

In some embodiments, the ethylene/α-olefin interpolymers have a heat offusion of less than 85 J/g and/or a pellet blocking strength of equal toor less than 100 pounds/foot² (4800 Pa), preferably equal to or lessthan 50 lbs/ft² (2400 Pa), especially equal to or less than 5 lbs/ft²(240 Pa), and as low as 0 lbs/ft² (0 Pa).

In other embodiments, the ethylene/α-olefin interpolymers comprise, inpolymerized form, at least 50 mole percent ethylene and have a 70° C.compression set of less than 80 percent, preferably less than 70 percentor less than 60 percent, most preferably less than 40 to 50 percent anddown to close to zero percent.

In some embodiments, the multi-block copolymers possess a PDI fitting aSchultz-Flory distribution rather than a Poisson distribution. Thecopolymers are further characterized as having both a polydisperse blockdistribution and a polydisperse distribution of block sizes andpossessing a most probable distribution of block lengths. Preferredmulti-block copolymers are those containing 4 or more blocks or segmentsincluding terminal blocks. More preferably, the copolymers include atleast 5, 10 or 20 blocks or segments including terminal blocks.

In addition, the inventive block interpolymers have additionalcharacteristics or properties. In one aspect, the interpolymers,preferably comprising ethylene and one or more copolymerizablecomonomers in polymerized form, are characterized by multiple blocks orsegments of two or more polymerized monomer units differing in chemicalor physical properties (blocked interpolymer), most preferably amulti-block copolymer, said block interpolymer having a molecularfraction which elutes between 40° C. and 130° C. when fractionated usingTREF, characterized in that said fraction has a molar comonomer contenthigher, preferably at least 5 percent higher, more preferably at least10 percent higher, than that of a comparable random ethyleneinterpolymer fraction eluting between the same temperatures, whereinsaid comparable random ethylene interpolymer comprises the samecomonomer(s), and has a melt index, density, and molar comonomer content(based on the whole polymer) within 10 percent of that of the blockedinterpolymer. Preferably, the Mw/Mn of the comparable interpolymer isalso within 10 percent of that of the blocked interpolymer and/or thecomparable interpolymer has a total comonomer content within 10 weightpercent of that of the blocked interpolymer.

Comonomer content may be measured using any suitable technique, withtechniques based on nuclear magnetic resonance (“NMR”) spectroscopypreferred. Moreover, for polymers or blends of polymers havingrelatively broad TREF curves, the polymer is first fractionated usingTREF into fractions each having an eluted temperature range of 10° C. orless. That is, each eluted fraction has a collection temperature windowof 10° C. or less. Using this technique, said block interpolymers haveat least one such fraction having a higher molar comonomer content thana corresponding fraction of the comparable interpolymer.

In another aspect, the inventive polymer is an olefin interpolymer,preferably comprising ethylene and one or more copolymerizablecomonomers in polymerized form, characterized by multiple blocks (i.e.,at least two blocks) or segments of two or more polymerized monomerunits differing in chemical or physical properties (blockedinterpolymer), most preferably a multi-block copolymer, said blockinterpolymer having a peak (but not just a molecular fraction) whichelutes between 40° C. and 130° C. (but without collecting and/orisolating individual fractions), characterized in that said peak, has acomonomer content estimated by infra-red spectroscopy when expandedusing a full width/half maximum (FWHM) area calculation, has an averagemolar comonomer content higher, preferably at least 5 percent higher,more preferably at least 10 percent higher, than that of a comparablerandom ethylene interpolymer peak at the same elution temperature andexpanded using a full width/half maximum (FWHM) area calculation,wherein said comparable random ethylene interpolymer has the samecomonomer(s) and has a melt index, density, and molar comonomer content(based on the whole polymer) within 10 percent of that of the blockedinterpolymer. Preferably, the Mw/Mn of the comparable interpolymer isalso within 10 percent of that of the blocked interpolymer and/or thecomparable interpolymer has a total comonomer content within 10 weightpercent of that of the blocked interpolymer. The full width/half maximum(FWHM) calculation is based on the ratio of methyl to methylene responsearea [CH₃/CH₂] from the ATREF infra-red detector, wherein the tallest(highest) peak is identified from the base line, and then the FWHM areais determined. For a distribution measured using an ATREF peak, the FWHMarea is defined as the area under the curve between T₁ and T₂, where T₁and T₂ are points determined, to the left and right of the ATREF peak,by dividing the peak height by two, and then drawing a line horizontalto the base line, that intersects the left and right portions of theATREF curve. A calibration curve for comonomer content is made usingrandom ethylene/α-olefin copolymers, plotting comonomer content from NMRversus FWHM area ratio of the TREF peak. For this infra-red method, thecalibration curve is generated for the same comonomer type of interest.The comonomer content of TREF peak of the inventive polymer can bedetermined by referencing this calibration curve using its FWHMmethyl:methylene area ratio [CH₃/CH₂] of the TREF peak.

Comonomer content may be measured using any suitable technique, withtechniques based on nuclear magnetic resonance (NMR) spectroscopypreferred. Using this technique, said blocked interpolymer has highermolar comonomer content than a corresponding comparable interpolymer.

Preferably, for interpolymers of ethylene and 1-octene, the blockinterpolymer has a comonomer content of the TREF fraction elutingbetween 40 and 130° C. greater than or equal to the quantity (−0.2013)T+20.07, more preferably greater than or equal to the quantity (−0.2013)T+21.07, where T is the numerical value of the peak elution temperatureof the TREF fraction being compared, measured in ° C.

FIG. 4 graphically depicts an embodiment of the block interpolymers ofethylene and 1-octene where a plot of the comonomer content versus TREFelution temperature for several comparable ethylene/1-octeneinterpolymers (random copolymers) are fit to a line representing(−0.2013) T+20.07 (solid line). The line for the equation (−0.2013)T+21.07 is depicted by a dotted line. Also depicted are the comonomercontents for fractions of a block ethylene/1-octene interpolymersaccording to embodiments of the invention (multi-block copolymers). Allof the block interpolymer fractions have significantly higher 1-octenecontent than either line at equivalent elution temperatures. This resultis characteristic of the inventive interpolymer and is believed to bedue to the presence of differentiated blocks within the polymer chains,having both crystalline and amorphous nature.

FIG. 5 graphically displays the TREF curve and comonomer contents ofpolymer fractions for Example 5 and comparative F to be discussed below.The peak eluting from 40° C. to 130° C., preferably from 60° C. to 95°C. for both polymers is fractionated in 5° C. increments. Actual datafor three of the fractions for Example 5 are represented by triangles.The skilled artisan can appreciate that an appropriate calibration curvemay be constructed for interpolymers with differing comonomer contentfitted to the ATREF temperature values. Preferably, such calibrationcurve is obtained using comparative interpolymers of the same monomers,preferably random copolymers made using a metallocene or otherhomogeneous catalyst composition. The inventive interpolymers arecharacterized by a molar comonomer content greater than the valuedetermined from the calibration curve at the same ATREF elutiontemperature, preferably at least 5 percent greater, more preferably atleast 10 percent greater.

In addition to the above aspects and properties described herein, theinventive polymers can be characterized by one or more additionalcharacteristics. In one aspect, the inventive polymer is an olefininterpolymer, preferably comprising ethylene and one or morecopolymerizable comonomers in polymerized form, characterized bymultiple blocks or segments of two or more polymerized monomer unitsdiffering in chemical or physical properties (blocked interpolymer),most preferably a multi-block copolymer, said block interpolymer havinga molecular fraction which elutes between 40° C. and 130° C., whenfractionated using TREF increments, characterized in that said fractionhas a molar comonomer content higher, preferably at least 5 percenthigher, more preferably at least 10, 15, 20 or 25 percent higher, thanthat of a comparable random ethylene interpolymer fraction elutingbetween the same temperatures, wherein said comparable random ethyleneinterpolymer comprises the same comonomer(s), preferably it is the samecomonomer(s), and a melt index, density, and molar comonomer content(based on the whole polymer) within 10 percent of that of the blockedinterpolymer. Preferably, the Mw/Mn of the comparable interpolymer isalso within 10 percent of that of the blocked interpolymer and/or thecomparable interpolymer has a total comonomer content within 10 weightpercent of that of the blocked interpolymer.

Preferably, the above interpolymers are interpolymers of ethylene and atleast one α-olefin, especially those interpolymers having a wholepolymer density from about 0.855 to about 0.935 g/cm³, and moreespecially for polymers having more than about 1 mole percent comonomer,the blocked interpolymer has a comonomer content of the TREF fractioneluting between 40 and 130° C. greater than or equal to the quantity(−0.1356) T+13.89, more preferably greater than or equal to the quantity(−0.1356) T+14.93, and most preferably greater than or equal to thequantity (−0.2013)T+21.07, where T is the numerical value of the peakATREF elution temperature of the TREF fraction being compared, measuredin ° C.

In still another aspect, the inventive polymer is an olefininterpolymer, preferably comprising ethylene and one or morecopolymerizable comonomers in polymerized form, characterized bymultiple blocks or segments of two or more polymerized monomer unitsdiffering in chemical or physical properties (blocked interpolymer),most preferably a multi-block copolymer, said block interpolymer havinga molecular fraction which elutes between 40° C. and 130° C., whenfractionated using TREF increments, characterized in that every fractionhaving a comonomer content of at least about 6 mole percent, has amelting point greater than about 100° C. For those fractions having acomonomer content from about 3 mole percent to about 6 mole percent,every fraction has a DSC melting point of about 110° C. or higher. Morepreferably, said polymer fractions, having at least 1 mol percentcomonomer, has a DSC melting point that corresponds to the equation:

Tm≧(−5.5926)(mol percent comonomer in the fraction)+135.90.

In yet another aspect, the inventive polymer is an olefin interpolymer,preferably comprising ethylene and one or more copolymerizablecomonomers in polymerized form, characterized by multiple blocks orsegments of two or more polymerized monomer units differing in chemicalor physical properties (blocked interpolymer), most preferably amulti-block copolymer, said block interpolymer having a molecularfraction which elutes between 40° C. and 130° C., when fractionatedusing TREF increments, characterized in that every fraction that has anATREF elution temperature greater than or equal to about 76° C., has amelt enthalpy (heat of fusion) as measured by DSC, corresponding to theequation:

Heat of fusion (J/gm)≦(3.1718)(ATREF elution temperature inCelsius)−136.58,

The inventive block interpolymers have a molecular fraction which elutesbetween 40° C. and 130° C., when fractionated using TREF increments,characterized in that every fraction that has an ATREF elutiontemperature between 40° C. and less than about 76° C., has a meltenthalpy (heat of fusion) as measured by DSC, corresponding to theequation:

Heat of fusion (J/gm)≦(1.1312)(ATREF elution temperature inCelsius)+22.97.

ATREF Peak Comonomer Composition Measurement by Infra-Red Detector

The comonomer composition of the TREF peak can be measured using an IR4infra-red detector available from Polymer Char, Valencia, Spain(http://www.polymerchar.com/).

The “composition mode” of the detector is equipped with a measurementsensor (CH₂) and composition sensor (CH₃) that are fixed narrow bandinfra-red filters in the region of 2800-3000 cm⁻¹. The measurementsensor detects the methylene (CH₂) carbons on the polymer (whichdirectly relates to the polymer concentration in solution) while thecomposition sensor detects the methyl (CH₃) groups of the polymer. Themathematical ratio of the composition signal (CH₃) divided by themeasurement signal (CH₂) is sensitive to the comonomer content of themeasured polymer in solution and its response is calibrated with knownethylene alpha-olefin copolymer standards.

The detector when used with an ATREF instrument provides both aconcentration (CH₂) and composition (CH₃) signal response of the elutedpolymer during the TREF process. A polymer specific calibration can becreated by measuring the area ratio of the CH₃ to CH₂ for polymers withknown comonomer content (preferably measured by NMR). The comonomercontent of an ATREF peak of a polymer can be estimated by applying thereference calibration of the ratio of the areas for the individual CH₃and CH₂ response (i.e. area ratio CH₃/CH₂ versus comonomer content).

The area of the peaks can be calculated using a full width/half maximum(FWHM) calculation after applying the appropriate baselines to integratethe individual signal responses from the TREF chromatogram. The fullwidth/half maximum calculation is based on the ratio of methyl tomethylene response area [CH₃/CH₂] from the ATREF infra-red detector,wherein the tallest (highest) peak is identified from the base line, andthen the FWHM area is determined. For a distribution measured using anATREF peak, the FWHM area is defined as the area under the curve betweenT1 and T2, where T1 and T2 are points determined, to the left and rightof the ATREF peak, by dividing the peak height by two, and then drawinga line horizontal to the base line, that intersects the left and rightportions of the ATREF curve.

The application of infra-red spectroscopy to measure the comonomercontent of polymers in this ATREF-infra-red method is, in principle,similar to that of GPC/FTIR systems as described in the followingreferences: Markovich, Ronald P.; Hazlitt, Lonnie G.; Smith, Linley;“Development of gel-permeation chromatography-Fourier transform infraredspectroscopy for characterization of ethylene-based polyolefincopolymers”. Polymeric Materials Science and Engineering (1991), 65,98-100.; and Deslauriers, P. J.; Rohlfing, D. C.; Shieh, E. T.;“Quantifying short chain branching microstructures in ethylene-1-olefincopolymers using size exclusion chromatography and Fourier transforminfrared spectroscopy (SEC-FTIR)”, Polymer (2002), 43, 59-170, both ofwhich are incorporated by reference herein in their entirety.

It should be noted that while the TREF fractions in the abovedescription are obtained in a 5° C. increment, other temperatureincrements are possible. For instance, a TREF fraction could be in a 4°C. increment, a 3° C. increment, a 2° C. increment, or 1° C. increment.

For copolymers of ethylene and an α-olefin, the inventive polymerspreferably possess (1) a PDI of at least 1.3, more preferably at least1.5, at least 1.7, or at least 2.0, and most preferably at least 2.6, upto a maximum value of 5.0, more preferably up to a maximum of 3.5, andespecially up to a maximum of 2.7; (2) a heat of fusion of 80 J/g orless; (3) an ethylene content of at least 50 weight percent; (4) a glasstransition temperature, T_(g), of less than −25° C., more preferablyless than −30° C., and/or (5) one and only one T_(in).

Further, the inventive polymers can have, alone or in combination withany other properties disclosed herein, a storage modulus, G′, such thatlog(G′) is greater than or equal to 400 kPa, preferably greater than orequal to 1.0 MPa, at a temperature of 100° C. Moreover, the inventivepolymers possess a relatively flat storage modulus as a function oftemperature in the range from 0 to 100° C. (illustrated in FIG. 6) thatis characteristic of block copolymers, and heretofore unknown for anolefin copolymer, especially a copolymer of ethylene and one or moreC₃₋₈ aliphatic α-olefins. (By the term “relatively flat” in this contextis meant that log G′ (in Pascals) decreases by less than one order ofmagnitude between 50 and 100° C., preferably between 0 and 100° C.).

The inventive interpolymers may be further characterized by athermomechanical analysis penetration depth of 1 mm at a temperature ofat least 90° C. as well as a flexural modulus of from 3 kpsi (20 MPa) to13 kpsi (90 MPa). Alternatively, the inventive interpolymers can have athermomechanical analysis penetration depth of 1 mm at a temperature ofat least 104° C. as well as a flexural modulus of at least 3 kpsi (20MPa). They may be characterized as having an abrasion resistance (orvolume loss) of less than 90 mm³. FIG. 7 shows the TMA (1 mm) versusflex modulus for the inventive polymers, as compared to other knownpolymers. The inventive polymers have significantly betterflexibility-heat resistance balance than the other polymers.

Additionally, the ethylene/α-olefin interpolymers can have a melt index,I₂, from 0.01 to 2000 g/10 minutes, preferably from 0.01 to 1000 g/10minutes, more preferably from 0.01 to 500 g/10 minutes, and especiallyfrom 0.01 to 100 g/10 minutes. In certain embodiments, theethylene/α-olefin interpolymers have a melt index, I₂, from 0.01 to 10g/10 minutes, from 0.5 to 50 g/10 minutes, from 1 to 30 g/10 minutes,from 1 to 6 g/10 minutes or from 0.3 to 10 g/10 minutes. In certainembodiments, the melt index for the ethylene/α-olefin polymers is 1 g/10minutes, 3 g/10 minutes or 5 g/10 minutes.

The polymers can have molecular weights, M_(W), from 1,000 g/mole to5,000,000 g/mole, preferably from 1000 g/mole to 1,000,000, morepreferably from 10,000 g/mole to 500,000 g/mole, and especially from10,000 g/mole to 300,000 g/mole. The density of the inventive polymerscan be from 0.80 to 0.99 g/cm³ and preferably for ethylene containingpolymers from 0.85 g/cm³ to 0.97 g/cm³. In certain embodiments, thedensity of the ethylene/α-olefin polymers ranges from 0.860 to 0.925g/cm³ or 0.867 to 0.910 g/cm³.

The process of making the polymers has been disclosed in the followingpatent applications: U.S. Provisional Application No. 60/553,906, filedMar. 17, 2004; U.S. Provisional Application No. 60/662,937, filed Mar.17, 2005; U.S. Provisional Application No. 60/662,939, filed Mar. 17,2005; U.S. Provisional Application No. 60/566,2938, filed Mar. 17, 2005;PCT Application No. PCT/US2005/008916, filed Mar. 17, 2005; PCTApplication No. PCT/US2005/008915, filed Mar. 17, 2005; and PCTApplication No. PCT/US2005/008917, filed Mar. 17, 2005, all of which areincorporated by reference herein in their entirety. For example, onesuch method comprises contacting ethylene and optionally one or moreaddition polymerizable monomers other than ethylene under additionpolymerization conditions with a catalyst composition comprising:

the admixture or reaction product resulting from combining:

(A) a first olefin polymerization catalyst having a high comonomerincorporation index,

(B) a second olefin polymerization catalyst having a comonomerincorporation index less than 90 percent, preferably less than 50percent, most preferably less than 5 percent of the comonomerincorporation index of catalyst (A), and

(C) a chain shuttling agent.

Representative catalysts and chain shuttling agent are as follows.

Catalyst (A1) is[N-(2,6-di(1-methylethyl)phenyl)amido)(2-isopropylphenyl)(α-naphthalen-2-diyl(6-pyridin-2-diyl)methane)]hafniumdimethyl, prepared according to the teachings of WO 03/40195, U.S. Pat.No. 6,953,764 and No. 6,960,635, and WO 04/24740.

Catalyst (A2) is[N-(2,6-di(1-methylethyl)phenyl)amido)(2-methylphenyl)(1,2-phenylene-(6-pyridin-2-diyl)methane)]hafniumdimethyl, prepared according to the teachings of WO 03/40195, U.S. Pat.No. 6,953,764 and No. 6,960,635, and WO 04/24740.

Catalyst (A3) isbis[N,N′″-(2,4,6-tri(methylphenyl)amido)ethylenediamine]hafniumdibenzyl.

Catalyst (A4) isbis((2-oxoyl-3-(dibenzo-1H-pyrrole-1-yl)-5-(methyl)phenyl)-2-phenoxymethyl)cyclohexane-1,2-diylzirconium (IV) dibenzyl, prepared substantially according to theteachings of U.S. Pat. No. 6,897,276.

Catalyst (B1) is1,2-bis-(3,5-di-t-butylphenylene)(1-(N-(1-methylethyl)immino)methyl)(2-oxoyl)zirconium dibenzyl

Catalyst (B2) is1,2-bis-(3,5-di-t-butylphenylene)(1-(N-(2-methylcyclohexyl)-immino)methyl)(2-oxoyl)zirconium dibenzyl

Catalyst (C1) is(t-butylamido)dimethyl(3-N-pyrrolyl-1,2,3,3a,7a-η-inden-1-yl)silanetitaniumdimethyl prepared substantially according to the techniques of U.S. Pat.No. 6,268,444:

Catalyst (C2) is (t-butylamido)di(4-methylphenyl)(2-methyl-1,2,3,3a,7a-η-inden-1-yl)silanetitanium dimethyl prepared substantiallyaccording to the teachings of U.S. Pat. No. 6,825,295:

Catalyst (C3) is(t-butylamido)di(4-methylphenyl)(2-methyl-1,2,3,3a,8a-η-s-indacen-1-yl)silanetitaniumdimethyl prepared substantially according to the teachings of U.S. Pat.No. 6,825,295:

Catalyst (D1) is bis(dimethyldisiloxane)(indene-1-yl)zirconiumdichloride available from Sigma-Aldrich:

Shuttling Agents The shuttling agents employed include diethylzinc,di(i-butyl)zinc, di(n-hexyl)zinc, triethylaluminum, trioctylaluminum,triethylgallium, i-butylaluminum bis(dimethyl(t-butyl)siloxane),i-butylaluminum bis(di(trimethylsilyl)amide), n-octylaluminumdi(pyridine-2-methoxide), bis(n-octadecyl)i-butylaluminum,i-butylaluminum bis(di(n-pentyl)amide), n-octylaluminumbis(2,6-di-t-butylphenoxide, n-octylaluminum di(ethyl(1-naphthyl)amide),ethylaluminum bis(t-butyldimethylsiloxide), ethylaluminumdi(bis(trimethylsilyl)amide), ethylaluminumbis(2,3,6,7-dibenzo-1-azacycloheptaneamide), n-octylaluminumbis(2,3,6,7-dibenzo-1-azacycloheptaneamide), n-octylaluminumbis(dimethyl(t-butyl)siloxide, ethylzinc (2,6-diphenylphenoxide), andethylzinc (t-butoxide).

Preferably, the foregoing process takes the form of a continuoussolution process for forming block copolymers, especially multi-blockcopolymers, preferably linear multi-block copolymers of two or moremonomers, more especially ethylene and a C₃₋₂₀ olefin or cycloolefin,and most especially ethylene and a C₄₋₂₀ α-olefin, using multiplecatalysts that are incapable of interconversion. That is, the catalystsare chemically distinct. Under continuous solution polymerizationconditions, the process is ideally suited for polymerization of mixturesof monomers at high monomer conversions. Under these polymerizationconditions, shuttling from the chain shuttling agent to the catalystbecomes advantaged compared to chain growth, and multi-block copolymers,especially linear multi-block copolymers are formed in high efficiency.

The inventive interpolymers may be differentiated from conventional,random copolymers, physical blends of polymers, and block copolymersprepared via sequential monomer addition, fluxional catalysts, anionicor cationic living polymerization techniques. In particular, compared toa random copolymer of the same monomers and monomer content atequivalent crystallinity or modulus, the inventive interpolymers havebetter (higher) heat resistance as measured by melting point, higher TMApenetration temperature, higher high-temperature tensile strength,and/or higher high-temperature torsion storage modulus as determined bydynamic mechanical analysis. Compared to a random copolymer containingthe same monomers and monomer content, the inventive interpolymers havelower compression set, particularly at elevated temperatures, lowerstress relaxation, higher creep resistance, higher tear strength, higherblocking resistance, faster setup due to higher crystallization(solidification) temperature, higher recovery (particularly at elevatedtemperatures), better abrasion resistance, higher retractive force, andbetter oil and filler acceptance.

The inventive interpolymers also exhibit a unique crystallization andbranching distribution relationship. That is, the inventiveinterpolymers have a relatively large difference between the tallestpeak temperature measured using CRYSTAF and DSC as a function of heat offusion, especially as compared to random copolymers containing the samemonomers and monomer level or physical blends of polymers, such as ablend of a high density polymer and a lower density copolymer, atequivalent overall density. It is believed that this unique feature ofthe inventive interpolymers is due to the unique distribution of thecomonomer in blocks within the polymer backbone. In particular, theinventive interpolymers may comprise alternating blocks of differingcomonomer content (including homopolymer blocks). The inventiveinterpolymers may also comprise a distribution in number and/or blocksize of polymer blocks of differing density or comonomer content, whichis a Schultz-Flory type of distribution. In addition, the inventiveinterpolymers also have a unique peak melting point and crystallizationtemperature profile that is substantially independent of polymerdensity, modulus, and morphology. In a preferred embodiment, themicrocrystalline order of the polymers demonstrates characteristicspherulites and lamellae that are distinguishable from random or blockcopolymers, even at PDI values that are less than 1.7, or even less than1.5, down to less than 1.3.

Moreover, the inventive interpolymers may be prepared using techniquesto influence the degree or level of blockiness. That is, the amount ofcomonomer and length of each polymer block or segment can be altered bycontrolling the ratio and type of catalysts and shuttling agent as wellas the temperature of the polymerization, and other polymerizationvariables. A surprising benefit of this phenomenon is the discovery thatas the degree of blockiness is increased, the optical properties, tearstrength, and high temperature recovery properties of the resultingpolymer are improved. In particular, haze decreases while clarity, tearstrength, and high temperature recovery properties increase as theaverage number of blocks in the polymer increases. By selectingshuttling agents and catalyst combinations having the desired chaintransferring ability (high rates of shuttling with low levels of chaintermination) other forms of polymer termination are effectivelysuppressed. Accordingly, little if any β-hydride elimination is observedin the polymerization of ethylene/α-olefin comonomer mixtures accordingto embodiments of the invention, and the resulting crystalline blocksare highly, or substantially completely, linear, possessing little or nolong chain branching.

Polymers with highly crystalline chain ends can be selectively preparedin accordance with embodiments of the invention. In elastomerapplications, reducing the relative quantity of polymer that terminateswith an amorphous block reduces the intermolecular dilutive effect oncrystalline regions. This result can be obtained by choosing chainshuttling agents and catalysts having an appropriate response tohydrogen or other chain terminating agents. Specifically, if thecatalyst which produces highly crystalline polymer is more susceptibleto chain termination (such as by use of hydrogen) than the catalystresponsible for producing the less crystalline polymer segment (such asthrough higher comonomer incorporation, regio-error, or atactic polymerformation), then the highly crystalline polymer segments willpreferentially populate the terminal portions of the polymer. Not onlyare the resulting terminated groups crystalline, but upon termination,the highly crystalline polymer forming catalyst site is once againavailable for reinitiation of polymer formation. The initially formedpolymer is therefore another highly crystalline polymer segment.Accordingly, both ends of the resulting multi-block copolymer arepreferentially highly crystalline.

The ethylene α-olefin interpolymers used in the embodiments of theinvention are preferably interpolymers of ethylene with at least oneC₃-C₂₀ α-olefin. Copolymers of ethylene and a C₃-C₂₀ α-olefin areespecially preferred. The interpolymers may further comprise C₄-C₁₈diolefin and/or alkenylbenzene. Suitable unsaturated comonomers usefulfor polymerizing with ethylene include, for example, ethylenicallyunsaturated monomers, conjugated or nonconjugated dienes, polyenes,alkenylbenzenes, etc. Examples of such comonomers include C₃-C₂₀α-olefins such as propylene, isobutylene, 1-butene, 1-hexene, 1-pentene,4-methyl-1-pentene, 1-heptene, 1-octene, 1-nonene, 1-decene, and thelike. 1-Butene and 1-octene are especially preferred. Other suitablemonomers include styrene, halo- or alkyl-substituted styrenes,vinylbenzocyclobutane, 1,4-hexadiene, 1,7-octadiene, and naphthenics(e.g., cyclopentene, cyclohexene and cyclooctene).

While ethylene/α-olefin interpolymers are preferred polymers, otherethylene/olefin polymers may also be used. Olefins as used herein referto a family of unsaturated hydrocarbon-based compounds with at least onecarbon-carbon double bond. Depending on the selection of catalysts, anyolefin may be used in embodiments of the invention. Preferably, suitableolefins are C₃-C₂₀ aliphatic and aromatic compounds containing vinylicunsaturation, as well as cyclic compounds, such as cyclobutene,cyclopentene, dicyclopentadiene, and norbornene, including but notlimited to, norbornene substituted in the 5 and 6 position with C₁-C₂₀hydrocarbyl or cyclohydrocarbyl groups. Also included are mixtures ofsuch olefins as well as mixtures of such olefins with C₄-C₄₀ diolefincompounds.

Examples of olefin monomers include, but are not limited to propylene,isobutylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene,1-nonene, 1-decene, and 1-dodecene, 1-tetradecene, 1-hexadecene,1-octadecene, 1-eicosene, 3-methyl-1-butene, 3-methyl-1-pentene,4-methyl-1-pentene, 4,6-dimethyl-1-heptene, 4-vinylcyclohexene,vinylcyclohexane, norbornadiene, ethylidene norbornene, cyclopentene,cyclohexene, dicyclopentadiene, cyclooctene, C₄-C₄₀ dienes, includingbut not limited to 1,3-butadiene, 1,3-pentadiene, 1,4-hexadiene,1,5-hexadiene, 1,7-octadiene, 1,9-decadiene, other C₄-C₄₀ α-olefins, andthe like. In certain embodiments, the α-olefin is propylene, 1-butene,1-pentene, 1-hexene, 1-octene or a combination thereof. Although anyhydrocarbon containing a vinyl group potentially may be used inembodiments of the invention, practical issues such as monomeravailability, cost, and the ability to conveniently remove unreactedmonomer from the resulting polymer may become more problematic as themolecular weight of the monomer becomes too high.

The polymerization processes described herein are well suited for theproduction of olefin polymers comprising monovinylidene aromaticmonomers including styrene, o-methyl styrene, p-methyl styrene,t-butylstyrene, and the like. In particular, interpolymers comprisingethylene and styrene can be prepared by following the teachings herein.Optionally, copolymers comprising ethylene, styrene and a C₃-C₂₀ alphaolefin, optionally comprising a C₄-C₂₀ diene, having improved propertiescan be prepared.

Suitable non-conjugated diene monomers can be a straight chain, branchedchain or cyclic hydrocarbon diene having from 6 to 15 carbon atoms.Examples of suitable non-conjugated dienes include, but are not limitedto, straight chain acyclic dienes, such as 1,4-hexadiene, 1,6-octadiene,1,7-octadiene, 1,9-decadiene, branched chain acyclic dienes, such as5-methyl-1,4-hexadiene; 3,7-dimethyl-1,6-octadiene;3,7-dimethyl-1,7-octadiene and mixed isomers of dihydromyricene anddihydroocinene, single ring alicyclic dienes, such as1,3-cyclopentadiene; 1,4-cyclohexadiene; 1,5-cyclooctadiene and1,5-cyclododecadiene, and multi-ring alicyclic fused and bridged ringdienes, such as tetrahydroindene, methyl tetrahydroindene,dicyclopentadiene, bicyclo-(2,2,1)-hepta-2,5-diene; alkenyl, alkylidene,cycloalkenyl and cycloalkylidene norbornenes, such as5-methylene-2-norbornene (MNB); 5-propenyl-2-norbornene,5-isopropylidene-2-norbornene, 5-(4-cyclopentenyl)-2-norbornene,5-cyclohexylidene-2-norbornene, 5-vinyl-2-norbornene, and norbornadiene.Of the dienes typically used to prepare EPDMs, the particularlypreferred dienes are 1,4-hexadiene (HD), 5-ethylidene-2-norbornene(ENB), 5-vinylidene-2-norbomene (VNB), 5-methylene-2-norbornene (MNB),and dicyclopentadiene (DCPD). The especially preferred dienes are5-ethylidene-2-norbornene (ENB) and 1,4-hexadiene (HD).

One class of desirable polymers that can be made in accordance withembodiments of the invention are elastomeric interpolymers of ethylene,a C₃-C₂₀ α-olefin, especially propylene, and optionally one or morediene monomers. Preferred α-olefins for use in this embodiment of thepresent invention are designated by the formula CH₂═CHR*, where R* is alinear or branched alkyl group of from 1 to 12 carbon atoms. Examples ofsuitable α-olefins include, but are not limited to, propylene,isobutylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, and1-octene. A particularly preferred α-olefin is propylene. The propylenebased polymers are generally referred to in the art as EP or EPDMpolymers. Suitable dienes for use in preparing such polymers, especiallymulti-block EPDM type polymers include conjugated or non-conjugated,straight or branched chain-, cyclic- or polycyclic-dienes comprisingfrom 4 to 20 carbons. Preferred dienes include 1,4-pentadiene,1,4-hexadiene, 5-ethylidene-2-norbornene, dicyclopentadiene,cyclohexadiene, and 5-butylidene-2-norbornene. A particularly preferreddiene is 5-ethylidene-2-norbornene.

Because the diene containing polymers comprise alternating segments orblocks containing greater or lesser quantities of the diene (includingnone) and α-olefin (including none), the total quantity of diene andα-olefin may be reduced without loss of subsequent polymer properties.That is, because the diene and α-olefin monomers are preferentiallyincorporated into one type of block of the polymer rather than uniformlyor randomly throughout the polymer, they are more efficiently utilizedand subsequently the crosslink density of the polymer can be bettercontrolled. Such crosslinkable elastomers and the cured products haveadvantaged properties, including higher tensile strength and betterelastic recovery.

In some embodiments, the inventive interpolymers made with two catalystsincorporating differing quantities of comonomer have a weight ratio ofblocks formed thereby from 95:5 to 5:95. The elastomeric polymersdesirably have an ethylene content of from 20 to 90 percent, a dienecontent of from 0.1 to 10 percent, and an α-olefin content of from 10 to80 percent, based on the total weight of the polymer. Furtherpreferably, the multi-block elastomeric polymers have an ethylenecontent of from 60 to 90 percent, a diene content of from 0.1 to 10percent, and an α-olefin content of from 10 to 40 percent, based on thetotal weight of the polymer. Preferred polymers are high molecularweight polymers, having a weight average molecular weight (Mw) from10,000 to about 2,500,000, preferably from 20,000 to 500,000, morepreferably from 20,000 to 350,000, and a polydispersity less than 3.5,more preferably less than 3.0, and a Mooney viscosity (ML (1+4) 125° C.)from 1 to 250. More preferably, such polymers have an ethylene contentfrom 65 to 75 percent, a diene content from 0 to 6 percent, and anα-olefin content from 20 to 35 percent.

The ethylene/α-olefin interpolymers can be functionalized byincorporating at least one functional group in its polymer structure.Exemplary functional groups may include, for example, ethylenicallyunsaturated mono- and di-functional carboxylic acids, ethylenicallyunsaturated mono- and di-functional carboxylic acid anhydrides, saltsthereof and esters thereof. Such functional groups may be grafted to anethylene/α-olefin interpolymer, or may be copolymerized with ethyleneand an optional additional comonomer to form an interpolymer ofethylene, the functional comonomer and optionally other comonomer(s).Means for grafting functional groups onto polyethylene are described forexample in U.S. Pat. Nos. 4,762,890, 4,927,888, and 4,950,541, thedisclosures of these patents are incorporated herein by reference intheir entirety. One particularly useful functional group is maleicanhydride.

The amount of the functional group present in the functionalinterpolymer can vary. The functional group can typically be present ina copolymer-type functionalized interpolymer in an amount of at leastabout 1.0 weight percent, preferably at least about 5 weight percent,and more preferably at least about 7 weight percent. The functionalgroup will typically be present in a copolymer-type functionalizedinterpolymer in an amount less than about 40 weight percent, preferablyless than about 30 weight percent, and more preferably less than about25 weight percent.

More on Block Index

Random copolymers satisfy the following relationship. See P. J. Flory,Trans. Faraday Soc., 51, 848 (1955), which is incorporated by referenceherein in its entirety.

$\begin{matrix}{{\frac{1}{T_{m}} - \frac{1}{T_{m}^{0}}} = {{- \left( \frac{R}{\Delta \; H_{u}} \right)}\ln \; P}} & (1)\end{matrix}$

In Equation 1, the mole fraction of crystallizable monomers, P, isrelated to the melting temperature, T_(m), of the copolymer and themelting temperature of the pure crystallizable homopolymer, T_(m) ⁰. Theequation is similar to the relationship for the natural logarithm of themole fraction of ethylene as a function of the reciprocal of the ATREFelution temperature (° K.) as shown in FIG. 8 for various homogeneouslybranched copolymers of ethylene and olefins.

As illustrated in FIG. 8, the relationship of ethylene mole fraction toATREF peak elution temperature and DSC melting temperature for varioushomogeneously branched copolymers is analogous to Flory's equation.Similarly, preparative TREF fractions of nearly all random copolymersand random copolymer blends likewise fall on this line, except for smallmolecular weight effects.

According to Flory, if P, the mole fraction of ethylene, is equal to theconditional probability that one ethylene unit will precede or followanother ethylene unit, then the polymer is random. On the other hand ifthe conditional probability that any 2 ethylene units occur sequentiallyis greater than P, then the copolymer is a block copolymer. Theremaining case where the conditional probability is less than P yieldsalternating copolymers.

The mole fraction of ethylene in random copolymers primarily determinesa specific distribution of ethylene segments whose crystallizationbehavior in turn is governed by the minimum equilibrium crystalthickness at a given temperature. Therefore, the copolymer melting andTREF crystallization temperatures of the inventive block copolymers arerelated to the magnitude of the deviation from the random relationshipin FIG. 8, and such deviation is a useful way to quantify how “blocky” agiven TREF fraction is relative to its random equivalent copolymer (orrandom equivalent TREF fraction). The term “blocky” refers to the extenta particular polymer fraction or polymer comprises blocks of polymerizedmonomers or comonomers. There are two random equivalents, onecorresponding to constant temperature and one corresponding to constantmole fraction of ethylene. These form the sides of a right triangle asshown in FIG. 9, which illustrates the definition of the block index.

In FIG. 9, the point (T_(X), P_(X)) represents a preparative TREFfraction, where the ATREF elution temperature, T_(X), and the NMRethylene mole fraction, P_(X), are measured values. The ethylene molefraction of the whole polymer, P_(AB), is also measured by NMR.

The “hard segment” elution temperature and mole fraction, (T_(A),P_(A)), can be estimated or else set to that of ethylene homopolymer forethylene copolymers. The TAB value corresponds to the calculated randomcopolymer equivalent ATREF elution temperature based on the measuredP_(AB). From the measured ATREF elution temperature, T_(X), thecorresponding random ethylene mole fraction, P_(X0), can also becalculated. The square of the block index is defined to be the ratio ofthe area of the (P_(X), T_(x)) triangle and the (T_(A), P_(AB))triangle. Since the right triangles are similar, the ratio of areas isalso the squared ratio of the distances from (T_(A), P_(AB)) and (T_(X),P_(x)) to the random line. In addition, the similarity of the righttriangles means the ratio of the lengths of either of the correspondingsides can be used instead of the areas.

${B\; I} = {{\frac{{1/T_{X}} - {1/T_{XO}}}{{1/T_{A}} - {1/T_{AB}}}\mspace{14mu} {or}\mspace{14mu} B\; I} = {- \frac{{{Ln}\; P_{X}} - {{Ln}\; P_{XO}}}{{{Ln}\; P_{A}} - {{Ln}\; P_{AB}}}}}$

It should be noted that the most perfect block distribution wouldcorrespond to a whole polymer with a single eluting fraction at thepoint (T_(A), P_(AB)), because such a polymer would preserve theethylene segment distribution in the “hard segment”, yet contain all theavailable octene (presumably in runs that are nearly identical to thoseproduced by the soft segment catalyst). In most cases, the “softsegment” will not crystallize in the ATREF (or preparative TREF).

Applications and End Uses

The inventive ethylene/α-olefin block interpolymers can be used in avariety of conventional thermoplastic fabrication processes to produceuseful articles, including objects comprising at least one film layer,such as a monolayer film, or at least one layer in a multilayer filmprepared by cast, blown, calendered, or extrusion coating processes;molded articles, such as blow molded, injection molded, or rotomoldedarticles; extrusions; fibers; and woven or non-woven fabrics.Thermoplastic compositions comprising the inventive polymers, includeblends with other natural or synthetic polymers, additives, reinforcingagents, ignition resistant additives, antioxidants, stabilizers,colorants, extenders, crosslinkers, blowing agents, and plasticizers. Ofparticular utility are multi-component fibers such as core/sheathfibers, having an outer surface layer, comprising at least in part, oneor more polymers according to embodiments of the invention.

Fibers that may be prepared from the inventive polymers or blendsinclude staple fibers, tow, multicomponent, sheath/core, twisted, andmonofilament. Suitable fiber forming processes include spinbonded, meltblown techniques, as disclosed in U.S. Pat. Nos. 4,430,563, 4,663,220,4,668,566, and 4,322,027, gel spun fibers as disclosed in U.S. Pat. No.4,413,110, woven and nonwoven fabrics, as disclosed in U.S. Pat. No.3,485,706, or structures made from such fibers, including blends withother fibers, such as polyester, nylon or cotton, thermoformed articles,extruded shapes, including profile extrusions and co-extrusions,calendared articles, and drawn, twisted, or crimped yarns or fibers. Thenew polymers described herein are also useful for wire and cable coatingoperations, as well as in sheet extrusion for vacuum forming operations,and forming molded articles, including the use of injection molding,blow molding process, or rotomolding processes. Compositions comprisingthe olefin polymers can also be formed into fabricated articles such asthose previously mentioned using conventional polyolefin processingtechniques which are well known to those skilled in the art ofpolyolefin processing.

Dispersions, both aqueous and non-aqueous, can also be formed using theinventive polymers or formulations comprising the same. Frothed foamscomprising the invented polymers can also be formed, as disclosed in PCTapplication No. PCT/US2004/027593, filed Aug. 25, 2004, and published asWO2005/021622. The polymers may also be crosslinked by any known means,such as the use of peroxide, electron beam, silane, azide, or othercross-linking technique. The polymers can also be chemically modified,such as by grafting (for example by use of maleic anhydride (MAH),silanes, or other grafting agent), halogenation, amination, sulfonation,or other chemical modification.

Additives and adjuvants may be included in any formulation comprisingthe inventive polymers. Suitable additives include fillers, such asorganic or inorganic particles, including clays, talc, titanium dioxide,zeolites, powdered metals, organic or inorganic fibers, including carbonfibers, silicon nitride fibers, steel wire or mesh, and nylon orpolyester cording, nano-sized particles, clays, and so forth;tackifiers, oil extenders, including paraffinic or napthelenic oils; andother natural and synthetic polymers, including other polymers accordingto embodiments of the invention.

Suitable polymers for blending with the polymers according toembodiments of the invention include thermoplastic and non-thermoplasticpolymers including natural and synthetic polymers. Exemplary polymersfor blending include polypropylene, (both impact modifyingpolypropylene, isotactic polypropylene, atactic polypropylene, andrandom ethylene/propylene copolymers), various types of polyethylene,including high pressure, free-radical LDPE, Ziegler Natta LLDPE,metallocene PE, including multiple reactor PE (“in reactor” blends ofZiegler-Natta PE and metallocene PE, such as products disclosed in U.S.Pat. Nos. 6,545,088, 6,538,070, 6,566,446, 5,844,045, 5,869,575, and6,448,341), ethylene-vinyl acetate (EVA), ethylene/vinyl alcoholcopolymers, polystyrene, impact modified polystyrene, ABS,styrene/butadiene block copolymers and hydrogenated derivatives thereof.(SBS and SEBS), and thermoplastic polyurethanes. Homogeneous polymerssuch as olefin plastomers and elastomers, ethylene and propylene-basedcopolymers (for example polymers available under the trade designationVERSIFY™ available from The Dow Chemical Company and VISTAMAXX™available from ExxonMobil Chemical Company can also be useful ascomponents in blends comprising the inventive polymers.

Suitable end uses for the foregoing products include elastic films andfibers; soft touch goods, such as tooth brush handles and appliancehandles; gaskets and profiles; adhesives (including hot melt adhesivesand pressure sensitive adhesives); footwear (including shoe soles andshoe liners); auto interior parts and profiles; foam goods (both openand closed cell); impact modifiers for other thermoplastic polymers suchas high density polyethylene, isotactic polypropylene, or other olefinpolymers; coated fabrics; hoses; tubing; weather stripping; cap liners;flooring; and viscosity index modifiers, also known as pour pointmodifiers, for lubricants.

In some embodiments, thermoplastic compositions comprising athermoplastic matrix polymer, especially isotactic polypropylene, and anelastomeric multi-block copolymer of ethylene and a copolymerizablecomonomer according to embodiments of the invention, are uniquelycapable of forming core-shell type particles having hard crystalline orsemi-crystalline blocks in the form of a core surrounded by soft orelastomeric blocks forming a “shell” around the occluded domains of hardpolymer. These particles are formed and dispersed within the matrixpolymer by the forces incurred during melt compounding or blending. Thishighly desirable morphology is believed to result due to the uniquephysical properties of the multi-block copolymers which enablecompatible polymer regions such as the matrix and higher comonomercontent elastomeric regions of the multi-block copolymer toself-assemble in the melt due to thermodynamic forces. Shearing forcesduring compounding are believed to produce separated regions of matrixpolymer encircled by elastomer. Upon solidifying, these regions becomeoccluded elastomer particles encased in the polymer matrix.

Particularly desirable blends are thermoplastic polyolefin blends (TPO),thermoplastic elastomer blends (TPE), thermoplastic vulcanizates (TPV)and styrenic polymer blends. TPE and TPV blends may be prepared bycombining the invented multi-block polymers, including functionalized orunsaturated derivatives thereof with an optional rubber, includingconventional block copolymers, especially an SBS block copolymer, andoptionally a crosslinking or vulcanizing agent. TPO blends are generallyprepared by blending the invented multi-block copolymers with apolyolefin, and optionally a crosslinking or vulcanizing agent. Theforegoing blends may be used in forming a molded object, and optionallycrosslinking the resulting molded article. A similar procedure usingdifferent components has been previously disclosed in U.S. Pat. No.6,797,779.

Suitable conventional block copolymers for this application desirablypossess a Mooney viscosity (ML 1+4 @ 100° C.) in the range from 10 to135, more preferably from 25 to 100, and most preferably from 30 to 80.Suitable polyolefins especially include linear or low densitypolyethylene, polypropylene (including atactic, isotactic, syndiotacticand impact modified versions thereof) and poly(4-methyl-1-pentene).Suitable styrenic polymers include polystyrene, rubber modifiedpolystyrene (HIPS), styrene/acrylonitrile copolymers (SAN), rubbermodified SAN (ABS or AES) and styrene maleic anhydride copolymers.

The blends may be prepared by mixing or kneading the respectivecomponents at a temperature around or above the melt point temperatureof one or both of the components. For most multiblock copolymers, thistemperature may be above 130° C., most generally above 145° C., and mostpreferably above 150° C. Typical polymer mixing or kneading equipmentthat is capable of reaching the desired temperatures and meltplastifying the mixture may be employed. These include mills, kneaders,extruders (both single screw and twin-screw), Banbury mixers, calenders,and the like. The sequence of mixing and method may depend on the finalcomposition. A combination of Banbury batch mixers and continuous mixersmay also be employed, such as a Banbury mixer followed by a mill mixerfollowed by an extruder. Typically, a TPE or TPV composition will have ahigher loading of cross-linkable polymer (typically the conventionalblock copolymer containing unsaturation) compared to TPO compositions.Generally, for TPE and TPV compositions, the weight ratio of blockcopolymer to multi-block copolymer may be from about 90:10 to 10:90,more preferably from 80:20 to 20:80, and most preferably from 75:25 to25:75. For TPO applications, the weight ratio of multi-block copolymerto polyolefin may be from about 49:51 to about 5:95, more preferablyfrom 35:65 to about 10:90. For modified styrenic polymer applications,the weight ratio of multi-block copolymer to polyolefin may also be fromabout 49:51 to about 5:95, more preferably from 35:65 to about 10:90.The ratios may be changed by changing the viscosity ratios of thevarious components. There is considerable literature illustratingtechniques for changing the phase continuity by changing the viscosityratios of the constituents of a blend that a person skilled in this artmay consult if necessary.

The blend compositions may contain processing oils, plasticizers, andprocessing aids. Rubber processing oils having a certain ASTMdesignation and paraffinic, napthenic or aromatic process oils are allsuitable for use. Generally from 0 to 150 parts, more preferably 0 to100 parts, and most preferably from 0 to 50 parts of oil per 100 partsof total polymer are employed. Higher amounts of oil may tend to improvethe processing of the resulting product at the expense of some physicalproperties. Additional processing aids include conventional waxes, fattyacid salts, such as calcium stearate or zinc stearate, (poly)alcoholsincluding glycols, (poly)alcohol ethers, including glycol ethers,(poly)esters, including (poly)glycol esters, and metal salt-, especiallyGroup 1 or 2 metal or zinc-, salt derivatives thereof.

It is known that non-hydrogenated rubbers such as those comprisingpolymerized forms of butadiene or isoprene, including block copolymers(here-in-after diene rubbers), have lower resistance to UV, ozone, andoxidation, compared to mostly or highly saturated rubbers. Inapplications such as tires made from compositions containing higherconcentrations of diene based rubbers, it is known to incorporate carbonblack to improve rubber stability, along with anti-ozone additives andanti-oxidants. Multi-block copolymers according to the present inventionpossessing extremely low levels of unsaturation, find particularapplication as a protective surface layer (coated, coextruded orlaminated) or weather resistant film adhered to articles formed fromconventional diene elastomer modified polymeric compositions.

For conventional TPO, TPV, and TPE applications, carbon black is theadditive of choice for UV absorption and stabilizing properties.Representative examples of carbon blacks include ASTM N110, N121, N220,N231, N234, N242, N293, N299, 5315, N326, N330, M332, N339, N343, N347,N351, N358, N375, N539, N550, N582, N630, N642, N650, N683, N754, N762,N765, N774, N787, N907, N908, N990 and N991. These carbon blacks haveiodine absorptions ranging from 9 to 145 g/kg and average pore volumesranging from 10 to 150 cm³/100 g. Generally, smaller particle sizedcarbon blacks are employed, to the extent cost considerations permit.For many such applications the present multi-block copolymers and blendsthereof require little or no carbon black, thereby allowing considerabledesign freedom to include alternative pigments or no pigments at all.Multi-hued tires or tires matching the color of the vehicle are onepossibility.

Compositions, including thermoplastic blends according to embodiments ofthe invention may also contain anti-ozonants or anti-oxidants that areknown to a rubber chemist of ordinary skill. The anti-ozonants may bephysical protectants such as waxy materials that come to the surface andprotect the part from oxygen or ozone or they may be chemical protectorsthat react with oxygen or ozone. Suitable chemical protectors includestyrenated phenols, butylated octylated phenol, butylateddi(dimethylbenzyl)phenol, p-phenylenediamines, butylated reactionproducts of p-cresol and dicyclopentadiene (DCPD), polyphenolicanitioxidants, hydroquinone derivatives, quinoline, diphenyleneantioxidants, thioester antioxidants, and blends thereof. Somerepresentative trade names of such products are Wingstay™ S antioxidant,Polystay™ 100 antioxidant, Polystay™ 100 AZ antioxidant, Polystay™ 200antioxidant, Wingstay™ L antioxidant, Wingstay™ LHLS antioxidant,Wingstay™ K antioxidant, Wingstay™ 29 antioxidant, Wingstay™ SN-1antioxidant, and Irganox™ antioxidants. In some applications, theanti-oxidants and anti-ozonants used will preferably be non-staining andnon-migratory.

For providing additional stability against UV radiation, hindered aminelight stabilizers (HALS) and UV absorbers may be also used. Suitableexamples include Tinuvin™ 123, Tinuvin™ 144, Tinuvin™ 622, Tinuvin™ 765,Tinuvin™ 770, and Tinuvin™ 780, available from Ciba Specialty Chemicals,and Chemisorb™ T944, available from Cytex Plastics, Houston Tex., USA. ALewis acid may be additionally included with a HALS compound in order toachieve superior surface quality, as disclosed in U.S. Pat. No.6,051,681.

For some compositions, additional mixing process may be employed topre-disperse the anti-oxidants, anti-ozonants, carbon black, UVabsorbers, and/or light stabilizers to form a masterbatch, andsubsequently to form polymer blends there from.

Suitable crosslinking agents (also referred to as curing or vulcanizingagents) for use herein include sulfur based, peroxide based, or phenolicbased compounds. Examples of the foregoing materials are found in theart, including in U.S. Pat. Nos. 3,758,643, 3,806,558, 5,051,478,4,104,210, 4,130,535, 4,202,801, 4,271,049, 4,340,684, 4,250,273,4,927,882, 4,311,628 and 5,248,729.

When sulfur based curing agents are employed, accelerators and cureactivators may be used as well. Accelerators are used to control thetime and/or temperature required for dynamic vulcanization and toimprove the properties of the resulting cross-linked article. In oneembodiment, a single accelerator or primary accelerator is used. Theprimary accelerator(s) may be used in total amounts ranging from about0.5 to about 4, preferably about 0.8 to about 1.5, phr, based on totalcomposition weight. In another embodiment, combinations of a primary anda secondary accelerator might be used with the secondary acceleratorbeing used in smaller amounts, such as from about 0.05 to about 3 phr,in order to activate and to improve the properties of the cured article.Combinations of accelerators generally produce articles havingproperties that are somewhat better than those produced by use of asingle accelerator. In addition, delayed action accelerators may be usedwhich are not affected by normal processing temperatures yet produce asatisfactory cure at ordinary vulcanization temperatures. Vulcanizationretarders might also be used. Suitable types of accelerators that may beused in the present invention are amines, disulfides, guanidines,thioureas, thiazoles, thiurams, sulfenamides, dithiocarbamates andxanthates. Preferably, the primary accelerator is a sulfenamide. If asecond accelerator is used, the secondary accelerator is preferably aguanidine, dithiocarbamate or thiuram compound. Certain processing aidsand cure activators such as stearic acid and ZnO may also be used. Whenperoxide based curing agents are used, co-activators or coagents may beused in combination therewith. Suitable coagents includetrimethylolpropane triacrylate (TMPTA), trimethylolpropanetrimethacrylate (TMPTMA), triallyl cyanurate (TAC), triallylisocyanurate (TAIC), among others. Use of peroxide crosslinkers andoptional coagents used for partial or complete dynamic vulcanization areknown in the art and disclosed for example in the publication, “PeroxideVulcanization of Elastomer”, Vol. 74, No 3, July-August 2001.

When the multi-block copolymer containing composition is at leastpartially crosslinked, the degree of crosslinking may be measured bydissolving the composition in a solvent for specified duration, andcalculating the percent gel or unextractable component. The percent gelnormally increases with increasing crosslinking levels. For curedarticles according to embodiments of the invention, the percent gelcontent is desirably in the range from 5 to 100 percent.

The multi-block copolymers according to embodiments of the invention aswell as blends thereof possess improved processability compared to priorart compositions, due, it is believed, to lower melt viscosity. Thus,the composition or blend demonstrates an improved surface appearance,especially when formed into a molded or extruded article. At the sametime, the present compositions and blends thereof uniquely possessimproved melt strength properties, thereby allowing the presentmulti-block copolymers and blends thereof, especially TPO blends, to beusefully employed in foam and thermoforming applications where meltstrength is currently inadequate.

Thermoplastic compositions according to embodiments of the invention mayalso contain organic or inorganic fillers or other additives such asstarch, talc, calcium carbonate, glass fibers, polymeric fibers(including nylon, rayon, cotton, polyester, and polyaramide), metalfibers, flakes or particles, expandable layered silicates, phosphates orcarbonates, such as clays, mica, silica, alumina, aluminosilicates oraluminophosphates, carbon whiskers, carbon fibers, nanoparticlesincluding nanotubes, wollastonite, graphite, zeolites, and ceramics,such as silicon carbide, silicon nitride or titania. Silane based orother coupling agents may also be employed for better filler bonding.

The thermoplastic compositions according to embodiments of theinvention, including the foregoing blends, may be processed byconventional molding techniques such as injection molding, extrusionmolding, thermoforming, slush molding, over molding, insert molding,blow molding, and other techniques. Films, including multi-layer films,may be produced by cast or tentering processes, including blown filmprocesses.

In addition to the above, the block ethylene/α-olefin interpolymers alsocan be used in a manner that is described in the following U.S.provisional applications, the disclosures of which and theircontinuations, divisional applications and continuation-in-partapplications are incorporated by reference herein in their entirety:

1) “Impact-Modification of Thermoplastics with Ethylene/α-Olefins”, U.S.Ser. No. 60/717,928, filed on Sep. 16, 2005;

2) “Three Dimensional Random Looped Structures Made from Interpolymersof Ethylene/α-Olefins and Uses Thereof', U.S. Ser. No. 60/718,130, filedon Sep. 16, 2005;

3) “Polymer Blends from Interpolymer of Ethylene/α-Olefin”, U.S. Ser.No. 60/717,825, filed on Sep. 16, 2005;

4) “Viscosity Index Improver for Lubricant Compositions”, U.S. Ser. No.60/718,129, filed on Sep. 16, 2005;

5) “Fibers Made from Copolymers of Ethylene/α-Olefins”, U.S. Ser. No.60/718,197, filed on Sep. 16, 2005;

6) “Fibers Made from Copolymers of Propylene/α-Olefins”, U.S. Ser. No.60/717,863, filed on Sep. 16, 2005;

7) “Adhesive and Marking Compositions Made from Interpolymers ofEthylene/α-Olefins”, U.S. Ser. No. 60/718,000, filed on Sep. 16, 2005;

8) “Compositions of Ethylene/α-Olefin Multi-Block Interpolymers SuitableFor Films”, U.S. Ser. No. 60/718,198, filed on Sep. 16, 2005;

9) “Rheology Modification of Interpolymers of Ethylene/α-Olefins andArticles Made Therefrom”, U.S. Ser. No. 60/718,036, filed on Sep. 16,2005;

10) “Soft Foams Made From Interpolymers of Ethylene/α-Olefins”, U.S.Ser. No. 60/717,893, filed on Sep. 16, 2005;

11) “Low Molecular Weight Ethylene/α-Olefin Interpolymer as BaseLubricant Oil”, U.S. Ser. No. 60/717,875, filed on Sep. 16, 2005;

12) “Foams Made From Interpolymers of Ethylene/α-Olefins”, U.S. Ser. No.60/717,860, filed on Sep. 16, 2005;

13) “Compositions of Ethylene/α-Olefin Multi-Block Interpolymer ForBlown Films with High Hot Tack”, U.S. Ser. No. 60/717,982, filed on Sep.16, 2005;

14) “Cap Liners, Closures and Gaskets From Multi-Block Polymers”, U.S.Ser. No. 60/717,824, filed on Sep. 16, 2005;

15) “Polymer Blends From Interpolymers of Ethylene/α-Olefins”, U.S. Ser.No. 60/718,245, filed on Sep. 16, 2005;

16) “Anti-Blocking Compositions Comprising Interpolymers ofEthylene/α-Olefins”, U.S. Ser. No. 60/717,588, filed on Sep. 16, 2005;

17) “Interpolymers of Ethylene/α-Olefins Blends and Profiles and GasketsMade Therefrom”, U.S. Ser. No. 60/718,165, filed on Sep. 16, 2005;

18) “Filled Polymer Compositions Made from Interpolymers ofEthylene/α-Olefins and Uses Thereof”, U.S. Ser. No. 60/717,587, filed onSep. 16, 2005;

19) “Compositions Of Ethylene/α-Olefin Multi-Block Interpolymer ForElastic Films and Laminates”, U.S. Ser. No. 60/718,081, filed on Sep.16, 2005;

20) “Thermoplastic Vulcanizate Comprising Interpolymers ofEthylene/α-Olefins”, U.S. Ser. No. 60/718,186, filed on Sep. 16, 2005;

21) “Multi-Layer, Elastic Articles”, U.S. Ser. No. 60/754,087, filed onDec. 27, 2005; and

22) “Functionalized Olefin Interpolymers, Compositions and ArticlesPrepared Therefrom, and Methods for Making the Same”, U.S. Ser. No.60/718,184, filed on Sep. 16, 2005.

EXAMPLES

The following examples are provided to illustrate the synthesis of theinventive polymers. Certain comparisons are made with some existingpolymers. The examples are presented to exemplify embodiments of theinvention but are not intended to limit the invention to the specificembodiments set forth. Unless indicated to the contrary, all parts andpercentages are by weight. All numerical values are approximate. Whennumerical ranges are given, it should be understood that embodimentsoutside the stated ranges may still fall within the scope of theinvention. Specific details described in each example should not beconstrued as necessary features of the invention.

Testing Methods

In the examples that follow, the following analytical techniques areemployed:

GPC Method for Samples 1-4 and A-C

An automated liquid-handling robot equipped with a heated needle set to160° C. is used to add enough 1,2,4-trichlorobenzene stabilized with 300ppm Ionol to each dried polymer sample to give a final concentration of30 mg/mL. A small glass stir rod is placed into each tube and thesamples are heated to 160° C. for 2 hours on a heated, orbital-shakerrotating at 250 rpm. The concentrated polymer solution is then dilutedto 1 mg/ml using the automated liquid-handling robot and the heatedneedle set to 160° C.

A Symyx Rapid GPC system is used to determine the molecular weight datafor each sample. A Gilson 350 pump set at 2.0 ml/min flow rate is usedto pump helium-purged 1,2-dichlorobenzene stabilized with 300 ppm Ionolas the mobile phase through three Plgel 10 micrometer (μm) Mixed B 300mm×7.5 mm columns placed in series and heated to 160° C. A Polymer LabsELS 1000 Detector is used with the Evaporator set to 250° C., theNebulizer set to 165° C., and the nitrogen flow rate set to 1.8 SLM at apressure of 60-80 psi (400−600 kPa) N₂. The polymer samples are heatedto 160° C. and each sample injected into a 250 μl loop using theliquid-handling robot and a heated needle. Serial analysis of thepolymer samples using two switched loops and overlapping injections areused. The sample data is collected and analyzed using Symyx Epoch™software. Peaks are manually integrated and the molecular weightinformation reported uncorrected against a polystyrene standardcalibration curve.

Standard CRYSTAF Method

Branching distributions are determined by crystallization analysisfractionation (CRYSTAF) using a CRYSTAF 200 unit commercially availablefrom PolymerChar, Valencia, Spain. The samples are dissolved in 1,2,4trichlorobenzene at 160° C. (0.66 mg/mL) for 1 hr and stabilized at 95°C. for 45 minutes. The sampling temperatures range from 95 to 30° C. ata cooling rate of 0.2° C./min. An infrared detector is used to measurethe polymer solution concentrations. The cumulative solubleconcentration is measured as the polymer crystallizes while thetemperature is decreased. The analytical derivative of the cumulativeprofile reflects the short chain branching distribution of the polymer.

The CRYSTAF peak temperature and area are identified by the peakanalysis module included in the CRYSTAF Software (Version 2001.b,PolymerChar, Valencia, Spain). The CRYSTAF peak finding routineidentifies a peak temperature as a maximum in the dW/dT curve and thearea between the largest positive inflections on either side of theidentified peak in the derivative curve. To calculate the CRYSTAF curve,the preferred processing parameters are with a temperature limit of 70°C. and with smoothing parameters above the temperature limit of 0.1, andbelow the temperature limit of 0.3.

DSC Standard Method (Excluding Samples 1-4 and A-C)

Differential Scanning Calorimetry results are determined using a TAImodel Q1000 DSC equipped with an RCS cooling accessory and anautosampler. A nitrogen purge gas flow of 50 ml/min is used. The sampleis pressed into a thin film and melted in the press at about 175° C. andthen air-cooled to room temperature (25° C.). 3-10 mg of material isthen cut into a 6 mm diameter disk, accurately weighed, placed in alight aluminum pan (ca 50 mg), and then crimped shut. The thermalbehavior of the sample is investigated with the following temperatureprofile. The sample is rapidly heated to 180° C. and held isothermal for3 minutes in order to remove any previous thermal history. The sample isthen cooled to −40° C. at 10° C./min cooling rate and held at −40° C.for 3 minutes. The sample is then heated to 150° C. at 10° C./min.heating rate. The cooling and second heating curves are recorded.

The DSC melting peak is measured as the maximum in heat flow rate (W/g)with respect to the linear baseline drawn between −30° C. and end ofmelting. The heat of fusion is measured as the area under the meltingcurve between −30° C. and the end of melting using a linear baseline.

Calibration of the DSC is done as follows. First, a baseline is obtainedby running a DSC from −90° C. without any sample in the aluminum DSCpan. Then 7 milligrams of a fresh indium sample is analyzed by heatingthe sample to 180° C., cooling the sample to 140° C. at a cooling rateof 10° C./min followed by keeping the sample isothermally at 140° C. for1 minute, followed by heating the sample from 140° C. to 180° C. at aheating rate of 10° C. per minute. The heat of fusion and the onset ofmelting of the indium sample are determined and checked to be within0.5° C. from 156.6° C. for the onset of melting and within 0.5 J/g from28.71 J/g for the of fusion. Then deionized water is analyzed by coolinga small drop of fresh sample in the DSC pan from 25° C. to −30° C. at acooling rate of 10° C. per minute. The sample is kept isothermally at−30° C. for 2 minutes and heat to 30° C. at a heating rate of 10° C. perminute. The onset of melting is determined and checked to be within 0.5°C. from 0° C.

GPC Method (Excluding Samples 1-4 and A-C)

The gel permeation chromatographic system consists of either a PolymerLaboratories Model PL-210 or a Polymer Laboratories Model PL-220instrument. The column and carousel compartments are operated at 140° C.Three Polymer Laboratories 10-micron Mixed-B columns are used. Thesolvent is 1,2,4 trichlorobenzene. The samples are prepared at aconcentration of 0.1 grams of polymer in 50 milliliters of solventcontaining 200 ppm of butylated hydroxytoluene (BHT). Samples areprepared by agitating lightly for 2 hours at 160° C. The injectionvolume used is 100 microliters and the flow rate is 1.0 ml/minute.

Calibration of the GPC column set is performed with 21 narrow molecularweight distribution polystyrene standards with molecular weights rangingfrom 580 to 8,400,000, arranged in 6 “cocktail” mixtures with at least adecade of separation between individual molecular weights. The standardsare purchased from Polymer Laboratories (Shropshire, UK). Thepolystyrene standards are prepared at 0.025 grams in 50 milliliters ofsolvent for molecular weights equal to or greater than 1,000,000, and0.05 grams in 50 milliliters of solvent for molecular weights less than1,000,000. The polystyrene standards are dissolved at 80° C. with gentleagitation for 30 minutes. The narrow standards mixtures are run firstand in order of decreasing highest molecular weight component tominimize degradation. The polystyrene standard peak molecular weightsare converted to polyethylene molecular weights using the followingequation (as described in Williams and Ward, J. Polym. Sci., Polym.Let., 6, 621 (1968)): M_(polyethylene)=0.431(M_(polystyrene)).

Polyethylene equivalent molecular weight calculations are performedusing Viscotek TriSEC software Version 3.0.

Compression Set

Compression set is measured according to ASTM D 395. The sample isprepared by stacking 25.4 mm diameter round discs of 3.2 mm, 2.0 mm, and0.25 mm thickness until a total thickness of 12.7 mm is reached. Thediscs are cut from 12.7 cm×12.7 cm compression molded plaques moldedwith a hot press under the following conditions: zero pressure for 3 minat 190° C., followed by 86 MPa for 2 min at 190° C., followed by coolinginside the press with cold running water at 86 MPa.

Density

Samples for density measurement are prepared according to ASTM D 1928.Measurements are made within one hour of sample pressing using ASTMD792, Method B.

Flexural/Secant Modulus/Storage Modulus

Samples are compression molded using ASTM D 1928. Flexural and 2 percentsecant moduli are measured according to ASTM D-790. Storage modulus ismeasured according to ASTM D 5026-01 or equivalent technique.

Optical Properties

Films of 0.4 mm thickness are compression molded using a hot press(Carver Model #4095-4PR1001R). The pellets are placed betweenpolytetrafluoroethylene sheets, heated at 190° C. at 55 psi (380 kPa)for 3 min, followed by 1.3 MPa for 3 min, and then 2.6 MPa for 3 min.The film is then cooled in the press with running cold water at 1.3 MPafor 1 min. The compression molded films are used for opticalmeasurements, tensile behavior, recovery, and stress relaxation.

Clarity is measured using BYK Gardner Haze-gard as specified in ASTM D1746.

45° gloss is measured using BYK Gardner Glossmeter Microgloss 45° asspecified in ASTM D-2457

Internal haze is measured using BYK Gardner Haze-gard based on ASTM D1003 Procedure A. Mineral oil is applied to the film surface to removesurface scratches.

Mechanical Properties—Tensile, Hysteresis, and Tear

Stress-strain behavior in uniaxial tension is measured using ASTM D 1708microtensile specimens. Samples are stretched with an Instron at 500%min⁻¹ at 21° C. Tensile strength and elongation at break are reportedfrom an average of 5 specimens.

100% and 300% Hysteresis is determined from cyclic loading to 100% and300% strains using ASTM D 1708 microtensile specimens with an Instron™instrument. The sample is loaded and unloaded at 267% min⁻¹ for 3 cyclesat 21° C. Cyclic experiments at 300% and 80° C. are conducted using anenvironmental chamber. In the 80° C. experiment, the sample is allowedto equilibrate for 45 minutes at the test temperature before testing. Inthe 21° C., 300% strain cyclic experiment, the retractive stress at 150%strain from the first unloading cycle is recorded. Percent recovery forall experiments are calculated from the first unloading cycle using thestrain at which the load returned to the base line. The percent recoveryis defined as:

${\% \mspace{14mu} {Recovery}} = {\frac{ɛ_{f} - ɛ_{s}}{ɛ_{f}} \times 100}$

where ε_(f) is the strain taken for cyclic loading and ε_(s) is thestrain where the load returns to the baseline during the 1^(st)unloading cycle.

Stress relaxation is measured at 50 percent strain and 37° C. for 12hours using an Instron™ instrument equipped with an environmentalchamber. The gauge geometry was 76 mm×25 mm×0.4 mm. After equilibratingat 37° C. for 45 min in the environmental chamber, the sample wasstretched to 50% strain at 333% min⁻¹. Stress was recorded as a functionof time for 12 hours. The percent stress relaxation after 12 hours wascalculated using the formula:

${\% \mspace{14mu} {Stress}\mspace{14mu} {Relaxation}} = {\frac{L_{0} - L_{12}}{L_{0}} \times 100}$

where L₀ is the load at 50% strain at 0 time and L₁₂ is the load at 50percent strain after 12 hours.

Tensile notched tear experiments are carried out on samples having adensity of 0.88 g/cc or less using an Instron™ instrument. The geometryconsists of a gauge section of 76 mm×13 mm×0.4 mm with a 2 mm notch cutinto the sample at half the specimen length. The sample is stretched at508 mm min⁻¹ at 21° C. until it breaks. The tear energy is calculated asthe area under the stress-elongation curve up to strain at maximum load.An average of at least 3 specimens are reported.

TMA

Thermal Mechanical Analysis (Penetration Temperature) is conducted on 30mm diameter×3.3 mm thick, compression molded discs, formed at 180° C.and 10 MPa molding pressure for 5 minutes and then air quenched. Theinstrument used is a TMA 7, brand available from Perkin-Elmer. In thetest, a probe with 1.5 mm radius tip (P/N N519-0416) is applied to thesurface of the sample disc with 1N force. The temperature is raised at5° C./min from 25° C. The probe penetration distance is measured as afunction of temperature. The experiment ends when the probe haspenetrated 1 mm into the sample.

DMA

Dynamic Mechanical Analysis (DMA) is measured on compression moldeddisks formed in a hot press at 180° C. at 10 MPa pressure for 5 minutesand then water cooled in the press at 90° C./min. Testing is conductedusing an ARES controlled strain rheometer (TA instruments) equipped withdual cantilever fixtures for torsion testing.

A 1.5 mm plaque is pressed and cut in a bar of dimensions 32×12 mm. Thesample is clamped at both ends between fixtures separated by 10 mm (gripseparation ΔL) and subjected to successive temperature steps from −100°C. to 200° C. (5° C. per step). At each temperature the torsion modulusG' is measured at an angular frequency of 10 rad/s, the strain amplitudebeing maintained between 0.1 percent and 4 percent to ensure that thetorque is sufficient and that the measurement remains in the linearregime.

An initial static force of 10 g is maintained (auto-tension mode) toprevent slack in the sample when thermal expansion occurs. As aconsequence, the grip separation ΔL increases with the temperature,particularly above the melting or softening point of the polymer sample.The test stops at the maximum temperature or when the gap between thefixtures reaches 65 mm.

Melt Index

Melt index, or I₂, is measured in accordance with ASTM D 1238, Condition190° C./2.16 kg. Melt index, or I₁₀ is also measured in accordance withASTM D 1238, Condition 190° C./10 kg.

ATREF

Analytical temperature rising elution fractionation (ATREF) analysis isconducted according to the method described in U.S. Pat. No. 4,798,081and Wilde, L.; Ryle, T. R.; Knobeloch, D. C.; Peat, I. R.; Determinationof Branching Distributions in Polyethylene and Ethylene Copolymers, J.Polym. Sci., 20, 441-455 (1982), which are incorporated by referenceherein in their entirety. The composition to be analyzed is dissolved intrichlorobenzene and allowed to crystallize in a column containing aninert support (stainless steel shot) by slowly reducing the temperatureto 20° C. at a cooling rate of 0.1° C./min. The column is equipped withan infrared detector. An ATREF chromatogram curve is then generated byeluting the crystallized polymer sample from the column by slowlyincreasing the temperature of the eluting solvent (trichlorobenzene)from 20 to 120° C. at a rate of 1.5° C./min.

¹³C NMR Analysis

The samples are prepared by adding approximately 3 g of a 50/50 mixtureof tetrachloroethane-d²/orthodichlorobenzene to 0.4 g sample in a 10 mmNMR tube. The samples are dissolved and homogenized by heating the tubeand its contents to 150° C. The data are collected using a JEOL Eclipse™400 MHz spectrometer or a Varian Unity Plus™ 400 MHz spectrometer,corresponding to a ¹³C resonance frequency of 100.5 MHz. The data areacquired using 4000 transients per data file with a 6 second pulserepetition delay. To achieve minimum signal-to-noise for quantitativeanalysis, multiple data files are added together. The spectral width is25,000 Hz with a minimum file size of 32K data points. The samples areanalyzed at 130° C. in a 10 mm broad band probe. The comonomerincorporation is determined using Randall's triad method (Randall, J.C.; JMS-Rev. Macromol. Chem. Phys., C29, 201-317 (1989), which isincorporated by reference herein in its entirety.

Polymer Fractionation by TREF (Also Known as Preparative TREF)

Large-scale TREF fractionation is carried by dissolving 15-20 g ofpolymer in 2 liters of 1,2,4-trichlorobenzene (TCB) by stirring for 4hours at 160° C. The polymer solution is forced by 15 psig (100 kPa)nitrogen onto a 3 inch by 4 foot (7.6 cm×12 cm) steel column packed witha 60:40 (v:v) mix of 30-40 mesh (600-425 μm) spherical, technicalquality glass beads (available from Potters Industries, HC 30 Box 20,Brownwood, Tex., 76801) and stainless steel, 0.028″ (0.7 mm) diametercut wire shot (available from Pellets, Inc. 63 Industrial Drive, NorthTonawanda, N.Y., 14120). The column is immersed in a thermallycontrolled oil jacket, set initially to 160° C. The column is firstcooled ballistically to 125° C., then slow cooled to 20° C. at 0.04° C.per minute and held for one hour. Fresh TCB is introduced at about 65ml/min while the temperature is increased at 0.167° C. per minute.

Approximately 2000 ml portions of eluant from the preparative TREFcolumn are collected in a 16 station, heated fraction collector. Thepolymer is concentrated in each fraction using a rotary evaporator untilabout 50 to 100 ml of the polymer solution remains. The concentratedsolutions are allowed to stand overnight before adding excess methanol,filtering, and rinsing (approx. 300-500 ml of methanol including thefinal rinse). The filtration step is performed on a 3 position vacuumassisted filtering station using 5.0 μm polytetrafluoroethylene coatedfilter paper (available from Osmonics Inc., Cat#Z50WP04750). Thefiltrated fractions are dried overnight in a vacuum oven at 60° C. andweighed on an analytical balance before further testing. Additionalinformation about hits method is taught in Wilde, L.; Ryle, T. R.;Knobeloch, D. C.; Peat, I. R.; Determination of Branching Distributionsin Polyethylene and Ethylene Copolymers, J. Polym. Sci., 20, 441-455(1982),

Melt Strength

Melt Strength (MS) is measured by using a capillary rheometer fittedwith a 2.1 mm diameter, 20:1 die with an entrance angle of approximately45 degrees. After equilibrating the samples at 190° C. for 10 minutes,the piston is run at a speed of 1 inch/minute (2.54 cm/minute). Thestandard test temperature is 190° C. The sample is drawn uniaxially to aset of accelerating nips located 100 mm below the die with anacceleration of 2.4 mm/sec². The required tensile force is recorded as afunction of the take-up speed of the nip rolls. The maximum tensileforce attained during the test is defined as the melt strength. In thecase of polymer melt exhibiting draw resonance, the tensile force beforethe onset of draw resonance was taken as melt strength. The meltstrength is recorded in centiNewtons (“cN”).

Catalysts

The term “overnight”, if used, refers to a time of approximately 16-18hours, the term “room temperature”, refers to a temperature of 20-25°C., and the term “mixed alkanes” refers to a commercially obtainedmixture of C₆₋₉ aliphatic hydrocarbons available under the tradedesignation Isopar E®, from ExxonMobil Chemical Company. In the eventthe name of a compound herein does not conform to the structuralrepresentation thereof, the structural representation shall control. Thesynthesis of all metal complexes and the preparation of all screeningexperiments were carried out in a dry nitrogen atmosphere using dry boxtechniques. All solvents used were HPLC grade and were dried beforetheir use.

MMAO refers to modified methylalumoxane, a triisobutylaluminum modifiedmethylalumoxane available commercially from Akzo-Noble Corporation.

The preparation of catalyst (B1) is conducted as follows.

a) Preparation of(1-methylethyl)(2-hydroxy-3,5-di(t-butyl)phenyl)methylimine

3,5-Di-t-butylsalicylaldehyde (3.00 g) is added to 10 mL ofisopropylamine. The solution rapidly turns bright yellow. After stirringat ambient temperature for 3 hours, volatiles are removed under vacuumto yield a bright yellow, crystalline solid (97 percent yield).

b) Preparation of1,2-bis-(3,5-di-t-butylphenylene)(1-(N-(1-methylethyl)immino)methyl)(2-oxoyl)zirconium dibenzyl

A solution of (1-methylethyl)(2-hydroxy-3,5-di(t-butyl)phenyl)imine (605mg, 2.2 mmol) in 5 mL toluene is slowly added to a solution ofZr(CH₂Ph)₄ (500 mg, 1.1 mmol) in 50 mL toluene. The resulting darkyellow solution is stirred for 30 min. Solvent is removed under reducedpressure to yield the desired product as a reddish-brown solid.

The preparation of catalyst (B2) is conducted as follows.

a) Preparation of(1-(2-methylcyclohexyl)ethyl)(2-oxoyl-3,5-di(t-butyl)phenyl)imine

2-Methylcyclohexylamine (8.44 mL, 64.0 mmol) is dissolved in methanol(90 mL), and di-t-butylsalicaldehyde (10.00 g, 42.67 mmol) is added. Thereaction mixture is stirred for three hours and then cooled to −25° C.for 12 hrs. The resulting yellow solid precipitate is collected byfiltration and washed with cold methanol (2×15 mL), and then dried underreduced pressure. The yield is 11.17 g of a yellow solid. ¹H NMR isconsistent with the desired product as a mixture of isomers.

b) Preparation ofbis-(1-(2-methylcyclohexyl)ethyl)(2-oxoyl-3,5-di(t-butyl)phenyl)immino)zirconium dibenzyl

A solution of(1-(2-methylcyclohexyl)ethyl)(2-oxoyl-3,5-di(t-butyl)phenyl)imine (7.63g, 23.2 mmol) in 200 mL toluene is slowly added to a solution ofZr(CH₂Ph)₄ (5.28 g, 11.6 mmol) in 600 mL toluene. The resulting darkyellow solution is stirred for 1 hour at 25° C. The solution is dilutedfurther with 680 mL toluene to give a solution having a concentration of0.00783 M.

Cocatalyst 1 A mixture of methyldi(C₁₄₋₁₈ alkyl)ammonium salts oftetrakis(pentafluorophenyl)borate (here-in-after armeenium borate),prepared by reaction of a long chain trialkylamine (Armeen™ M2HT,available from Akzo-Nobel, Inc.), HCl and Li[B(C₆F₅)₄], substantially asdisclosed in U.S. Pat. No. 5,919,9883, Ex. 2.

Cocatalyst 2 Mixed C₁₄₋₁₈ alkyldimethylammonium salt ofbis(tris(pentafluorophenyl)-alumane)-2-undecylimidazolide, preparedaccording to U.S. Pat. No. 6,395,671, Ex. 16.

Shuttling Agents The shuttling agents employed include diethylzinc (DEZ,SA1), di(i-butyl)zinc (SA2), di(n-hexyl)zinc (SA3), triethylaluminum(TEA, SA4), trioctylaluminum (SA5), triethylgallium (SA6),i-butylaluminum bis(dimethyl(t-butyl)siloxane) (SA7), i-butylaluminumbis(di(trimethylsilyl)amide) (SA8), n-octylaluminumdi(pyridine-2-methoxide) (SA9), bis(n-octadecyl)i-butylaluminum (SA10),i-butylaluminum bis(di(n-pentyl)amide) (SA11), n-octylaluminumbis(2,6-di-t-butylphenoxide) (SAl2), n-octylaluminumdi(ethyl(1-naphthyl)amide) (SA13), ethylaluminumbis(t-butyldimethylsiloxide) (SA14), ethylaluminumdi(bis(trimethylsilyl)amide) (SA15), ethylaluminumbis(2,3,6,7-dibenzo-1-azacycloheptaneamide) (SA16), n-octylaluminumbis(2,3,6,7-dibenzo-1-azacycloheptaneamide) (SA17), n-octylaluminumbis(dimethyl(t-butyl)siloxide(SA18), ethylzinc (2,6-diphenylphenoxide)(SA19), and ethylzinc (t-butoxide) (SA20).

Examples 1-4, Comparative A-C General High Throughput ParallelPolymerization Conditions

Polymerizations are conducted using a high throughput, parallelpolymerization reactor (PPR) available from Symyx Technologies, Inc. andoperated substantially according to U.S. Pat. Nos. 6,248,540, 6,030,917,6,362,309, 6,306,658, and 6,316,663. Ethylene copolymerizations areconducted at 130° C. and 200 psi (1.4 MPa) with ethylene on demand using1.2 equivalents of cocatalyst 1 based on total catalyst used (1.1equivalents when MMAO is present). A series of polymerizations areconducted in a parallel pressure reactor (PPR) contained of 48individual reactor cells in a 6×8 array that are fitted with apre-weighed glass tube. The working volume in each reactor cell is 6000μL. Each cell is temperature and pressure controlled with stirringprovided by individual stirring paddles. The monomer gas and quench gasare plumbed directly into the PPR unit and controlled by automaticvalves. Liquid reagents are robotically added to each reactor cell bysyringes and the reservoir solvent is mixed alkanes. The order ofaddition is mixed alkanes solvent (4 ml), ethylene, 1-octene comonomer(1 ml), cocatalyst 1 or cocatalyst 1/MMAO mixture, shuttling agent, andcatalyst or catalyst mixture. When a mixture of cocatalyst 1 and MMAO ora mixture of two catalysts is used, the reagents are premixed in a smallvial immediately prior to addition to the reactor. When a reagent isomitted in an experiment, the above order of addition is otherwisemaintained. Polymerizations are conducted for approximately 1-2 minutes,until predetermined ethylene consumptions are reached. After quenchingwith CO, the reactors are cooled and the glass tubes are unloaded. Thetubes are transferred to a centrifuge/vacuum drying unit, and dried for12 hours at 60° C. The tubes containing dried polymer are weighed andthe difference between this weight and the tare weight gives the netyield of polymer. Results are contained in Table 1. In Table 1 andelsewhere in the application, comparative compounds are indicated by anasterisk (*).

Examples 1-4 demonstrate the synthesis of linear block copolymers by thepresent invention as evidenced by the formation of a very narrow MWD,essentially monomodal copolymer when DEZ is present and a bimodal, broadmolecular weight distribution product (a mixture of separately producedpolymers) in the absence of DEZ. Due to the fact that Catalyst (A 1) isknown to incorporate more octene than Catalyst (B1), the differentblocks or segments of the resulting copolymers according to embodimentsof the invention are distinguishable based on branching or density.

TABLE 1 Cat. (A1) Cat (B1) Cocat MMAO shuttling Ex. (μmol) (μmol) (μmol)(μmol) agent (μmol) Yield (g) Mn Mw/Mn hexyls¹ A* 0.06 — 0.066 0.3 —0.1363 300502 3.32 — B* — 0.1 0.110 0.5 — 0.1581 36957 1.22 2.5 C* 0.060.1 0.176 0.8 — 0.2038 45526 5.30² 5.5 1 0.06 0.1 0.192 — DEZ (8.0)0.1974 28715 1.19 4.8 2 0.06 0.1 0.192 — DEZ (80.0) 0.1468 2161 1.1214.4 3 0.06 0.1 0.192 — TEA (8.0) 0.208 22675 1.71 4.6 4 0.06 0.1 0.192— TEA (80.0) 0.1879 3338 1.54 9.4 ¹C₆ or higher chain content per 1000carbons ²Bimodal molecular weight distribution

It may be seen the polymers produced according to embodiments of theinvention have a relatively narrow polydispersity (Mw/Mn) and largerblock-copolymer content (trimer, tetramer, or larger) than polymersprepared in the absence of the shuttling agent.

Further characterizing data for the polymers of Table 1 are determinedby reference to the figures. More specifically DSC and ATREF resultsshow the following:

The DSC curve for the polymer of example 1 shows a 115.7° C. meltingpoint (Tm) with a heat of fusion of 158.1 J/g. The corresponding CRYSTAFcurve shows the tallest peak at 34.5° C. with a peak area of 52.9percent. The difference between the DSC Tm and the Tcrystaf is 81.2° C.

The DSC curve for the polymer of example 2 shows a peak with a 109.7° C.melting point (Tm) with a heat of fusion of 214.0 J/g. The correspondingCRYSTAF curve shows the tallest peak at 46.2° C. with a peak area of57.0 percent. The difference between the DSC Tm and the Tcrystaf is63.5° C.

The DSC curve for the polymer of example 3 shows a peak with a 120.7° C.melting point (Tm) with a heat of fusion of 160.1 J/g. The correspondingCRYSTAF curve shows the tallest peak at 66.1° C. with a peak area of71.8 percent. The difference between the DSC Tm and the Tcrystaf is54.6° C.

The DSC curve for the polymer of example 4 shows a peak with a 104.5° C.melting point (Tm) with a heat of fusion of 170.7 J/g. The correspondingCRYSTAF curve shows the tallest peak at 30° C. with a peak area of 18.2percent. The difference between the DSC Tm and the Tcrystaf is 74.5° C.

The DSC curve for comparative A shows a 90.0° C. melting point (Tm) witha heat of fusion of 86.7 J/g. The corresponding CRYSTAF curve shows thetallest peak at 48.5° C. with a peak area of 29.4 percent. Both of thesevalues are consistent with a resin that is low in density. Thedifference between the DSC Tm and the Tcrystaf is 41.8° C.

The DSC curve for comparative B shows a 129.8° C. melting point (Tm)with a heat of fusion of 237.0 J/g. The corresponding CRYSTAF curveshows the tallest peak at 82.4° C. with a peak area of 83.7 percent.Both of these values are consistent with a resin that is high indensity. The difference between the DSC Tm and the Tcrystaf is 47.4° C.

The DSC curve for comparative C shows a 125.3° C. melting point (Tm)with a heat of fusion of 143.0 J/g. The corresponding CRYSTAF curveshows the tallest peak at 81.8° C. with a peak area of 34.7 percent aswell as a lower crystalline peak at 52.4° C. The separation between thetwo peaks is consistent with the presence of a high crystalline and alow crystalline polymer. The difference between the DSC Tm and theTcrystaf is 43.5° C.

Examples 5-19, Comparatives D-F, Continuous Solution Polymerization,Catalyst A1/B2+DEZ

Continuous solution polymerizations are carried out in a computercontrolled autoclave reactor equipped with an internal stirrer. Purifiedmixed alkanes solvent (Isopar™E available from ExxonMobil ChemicalCompany), ethylene at 2.70 lbs/hour (1.22 kg/hour), 1-octene, andhydrogen (where used) are supplied to a 3.8 L reactor equipped with ajacket for temperature control and an internal thermocouple. The solventfeed to the reactor is measured by a mass-flow controller. A variablespeed diaphragm pump controls the solvent flow rate and pressure to thereactor. At the discharge of the pump, a side stream is taken to provideflush flows for the catalyst and cocatalyst 1 injection lines and thereactor agitator. These flows are measured by Micro-Motion mass flowmeters and controlled by control valves or by the manual adjustment ofneedle valves. The remaining solvent is combined with 1-octene,ethylene, and hydrogen (where used) and fed to the reactor. A mass flowcontroller is used to deliver hydrogen to the reactor as needed. Thetemperature of the solvent/monomer solution is controlled by use of aheat exchanger before entering the reactor. This stream enters thebottom of the reactor. The catalyst component solutions are meteredusing pumps and mass flow meters and are combined with the catalystflush solvent and introduced into the bottom of the reactor. The reactoris run liquid-full at 500 psig (3.45 MPa) with vigorous stirring.Product is removed through exit lines at the top of the reactor. Allexit lines from the reactor are steam traced and insulated.Polymerization is stopped by the addition of a small amount of waterinto the exit line along with any stabilizers or other additives andpassing the mixture through a static mixer. The product stream is thenheated by passing through a heat exchanger before devolatilization. Thepolymer product is recovered by extrusion using a devolatilizingextruder and water cooled pelletizer. Process details and results arecontained in Table 2. Selected polymer properties are provided in Table3.

TABLE 2 Process details for preparation of exemplary polymers Cat Cat A1Cat DEZ Cocat Cocat Poly C₈H₁₆ Solv. H₂ T A1² Flow B2³ B2 Flow DEZ FlowConc. Flow [C₂H₄]/ Rate⁵ Conv Ex. kg/hr kg/hr sccm¹ ° C. ppm kg/hr ppmkg/hr Conc % kg/hr ppm kg/hr [DEZ]⁴ kg/hr %⁶ Solids % Eff.⁷ D* 1.63 12.729.90 120 142.2  0.14 — — 0.19 0.32  820 0.17 536 1.81 88.8 11.2 95.2 E*″  9.5 5.00 ″ — — 109 0.10 0.19 ″ 1743 0.40 485 1.47 89.9 11.3 126.8 F*″ 11.3 251.6 ″ 71.7 0.06 30.8 0.06 — — ″ 0.11 — 1.55 88.5 10.3 257.7  5″ ″ — ″ ″ 0.14 30.8 0.13 0.17 0.43 ″ 0.26 419 1.64 89.6 11.1 118.3  6 ″″ 4.92 ″ ″ 0.10 30.4 0.08 0.17 0.32 ″ 0.18 570 1.65 89.3 11.1 172.7  7 ″″ 21.70 ″ ″ 0.07 30.8 0.06 0.17 0.25 ″ 0.13 718 1.60 89.2 10.6 244.1  8″ ″ 36.90 ″ ″ 0.06 ″ ″ ″ 0.10 ″ 0.12 1778 1.62 90.0 10.8 261.1  9 ″ ″78.43 ″ ″ ″ ″ ″ ″ 0.04 ″ ″ 4596 1.63 90.2 10.8 267.9 10 ″ ″ 0.00 12371.1 0.12 30.3 0.14 0.34 0.19 1743 0.08 415 1.67 90.31 11.1 131.1 11 ″ ″″ 120 71.1 0.16 ″ 0.17 0.80 0.15 1743 0.10 249 1.68 89.56 11.1 100.6 12″ ″ ″ 121 71.1 0.15 ″ 0.07 ″ 0.09 1743 0.07 396 1.70 90.02 11.3 137.0 13″ ″ ″ 122 71.1 0.12 ″ 0.06 ″ 0.05 1743 0.05 653 1.69 89.64 11.2 161.9 14″ ″ ″ 120 71.1 0.05 ″ 0.29 ″ 0.10 1743 0.10 395 1.41 89.42 9.3 114.1 152.45 ″ ″ ″ 71.1 0.14 ″ 0.17 ″ 0.14 1743 0.09 282 1.80 89.33 11.3 121.316 ″ ″ ″ 122 71.1 0.10 ″ 0.13 ″ 0.07 1743 0.07 485 1.78 90.11 11.2 159.717 ″ ″ ″ 121 71.1 0.10 ″ 0.14 ″ 0.08 1743 ″ 506 1.75 89.08 11.0 155.6 180.69 ″ ″ 121 71.1 ″ ″ 0.22 ″ 0.11 1743 0.10 331 1.25 89.93 8.8 90.2 190.32 ″ ″ 122 71.1 0.06 ″ ″ ″ 0.09 1743 0.08 367 1.16 90.74 8.4 106.0*Comparative, not an example of the invention ¹standard cm³/min²[N-(2,6-di(1-methylethyl)phenyl)amido)(2-isopropylphenyl)(α-naphthalen-2-diyl(6-pyridin-2-diyl)methane)]hafniumdimethyl³bis-(1-(2-methylcyclohexyl)ethyl)(2-oxoyl-3,5-di(t-butyl)phenyl)immino)zirconium dibenzyl ⁴molar ratio in reactor ⁵polymer production rate⁶percent ethylene conversion in reactor ⁷efficiency, kg polymer/g Mwhere g M = g Hf + g Zr

TABLE 3 Properties of exemplary polymers Heat of Tm − CRYSTAF Density MwMn Fusion T_(m) T_(c) T_(CRYSTAF) T_(CRYSTAF) Peak Area Ex. (g/cm³) I₂I₁₀ I₁₀/I₂ (g/mol) (g/mol) Mw/Mn (J/g) (° C.) (° C.) (° C.) (° C.)(percent) D* 0.8627 1.5 10.0 6.5 110,000 55,800 2.0 32 37 45 30 7 99 E*0.9378 7.0 39.0 5.6 65,000 33,300 2.0 183 124 113 79 45 95 F* 0.8895 0.912.5 13.4 137,300 9,980 13.8 90 125 111 78 47 20  5 0.8786 1.5 9.8 6.7104,600 53,200 2.0 55 120 101 48 72 60  6 0.8785 1.1 7.5 6.5 10960053300 2.1 55 115 94 44 71 63  7 0.8825 1.0 7.2 7.1 118,500 53,100 2.2 69121 103 49 72 29  8 0.8828 0.9 6.8 7.7 129,000 40,100 3.2 68 124 106 8043 13  9 0.8836 1.1 9.7 9.1 129600 28700 4.5 74 125 109 81 44 16 100.8784 1.2 7.5 6.5 113,100 58,200 1.9 54 116 92 41 75 52 11 0.8818 9.159.2 6.5 66,200 36,500 1.8 63 114 93 40 74 25 12 0.8700 2.1 13.2 6.4101,500 55,100 1.8 40 113 80 30 83 91 13 0.8718 0.7 4.4 6.5 132,10063,600 2.1 42 114 80 30 81 8 14 0.9116 2.6 15.6 6.0 81,900 43,600 1.9123 121 106 73 48 92 15 0.8719 6.0 41.6 6.9 79,900 40,100 2.0 33 114 9132 82 10 16 0.8758 0.5 3.4 7.1 148,500 74,900 2.0 43 117 96 48 69 65 170.8757 1.7 11.3 6.8 107,500 54,000 2.0 43 116 96 43 73 57 18 0.9192 4.124.9 6.1 72,000 37,900 1.9 136 120 106 70 50 94 19 0.9344 3.4 20.3 6.076,800 39,400 1.9 169 125 112 80 45 88

The resulting polymers are tested by DSC and ATREF as with previousexamples. Results are as follows:

The DSC curve for the polymer of example 5 shows a peak with a 119.6° C.melting point (Tm) with a heat of fusion of 60.0 J/g. The correspondingCRYSTAF curve shows the tallest peak at 47.6° C. with a peak area of59.5 percent. The delta between the DSC Tm and the Tcrystaf is 72.0° C.

The DSC curve for the polymer of example 6 shows a peak with a 115.2° C.melting point (Tm) with a heat of fusion of 60.4 J/g. The correspondingCRYSTAF curve shows the tallest peak at 44.2° C. with a peak area of62.7 percent. The delta between the DSC Tm and the Tcrystaf is 71.0° C.

The DSC curve for the polymer of example 7 shows a peak with a 121.3° C.melting point with a heat of fusion of 69.1 J/g. The correspondingCRYSTAF curve shows the tallest peak at 49.2° C. with a peak area of29.4 percent. The delta between the DSC Tm and the Tcrystaf is 72.1° C.

The DSC curve for the polymer of example 8 shows a peak with a 123.5° C.melting point (Tm) with a heat of fusion of 67.9 J/g. The correspondingCRYSTAF curve shows the tallest peak at 80.1° C. with a peak area of12.7 percent. The delta between the DSC Tm and the Tcrystaf is 43.4° C.

The DSC curve for the polymer of example 9 shows a peak with a 124.6° C.melting point (Tm) with a heat of fusion of 73.5 J/g. The correspondingCRYSTAF curve shows the tallest peak at 80.8° C. with a peak area of16.0 percent. The delta between the DSC Tm and the Tcrystaf is 43.8° C.

The DSC curve for the polymer of example 10 shows a peak with a 115.6°C. melting point (Tm) with a heat of fusion of 60.7 J/g. Thecorresponding CRYSTAF curve shows the tallest peak at 40.9° C. with apeak area of 52.4 percent. The delta between the DSC Tm and the Tcrystafis 74.7° C.

The DSC curve for the polymer of example 11 shows a peak with a 113.6°C. melting point (Tm) with a heat of fusion of 70.4 J/g. Thecorresponding CRYSTAF curve shows the tallest peak at 39.6° C. with apeak area of 25.2 percent. The delta between the DSC Tm and the Tcrystafis 74.1° C.

The DSC curve for the polymer of example 12 shows a peak with a 113.2°C. melting point (Tm) with a heat of fusion of 48.9 J/g. Thecorresponding CRYSTAF curve shows no peak equal to or above 30° C.(Tcrystaf for purposes of further calculation is therefore set at 30°C.). The delta between the DSC Tm and the Tcrystaf is 83.2° C.

The DSC curve for the polymer of example 13 shows a peak with a 114.4°C. melting point (Tm) with a heat of fusion of 49.4 J/g. Thecorresponding CRYSTAF curve shows the tallest peak at 33.8° C. with apeak area of 7.7 percent. The delta between the DSC Tm and the Tcrystafis 84.4° C.

The DSC for the polymer of example 14 shows a peak with a 120.8° C.melting point (Tm) with a heat of fusion of 127.9 J/g. The correspondingCRYSTAF curve shows the tallest peak at 72.9° C. with a peak area of92.2 percent. The delta between the DSC Tm and the Tcrystaf is 47.9° C.

The DSC curve for the polymer of example 15 shows a peak with a 114.3°C. melting point (Tm) with a heat of fusion of 36.2 J/g. Thecorresponding CRYSTAF curve shows the tallest peak at 32.3° C. with apeak area of 9.8 percent. The delta between the DSC Tm and the Tcrystafis 82.0° C.

The DSC curve for the polymer of example 16 shows a peak with a 116.6°C. melting point (Tm) with a heat of fusion of 44.9 J/g. Thecorresponding CRYSTAF curve shows the tallest peak at 48.0° C. with apeak area of 65.0 percent. The delta between the DSC Tm and the Tcrystafis 68.6° C.

The DSC curve for the polymer of example 17 shows a peak with a 116.0°C. melting point (Tm) with a heat of fusion of 47.0 J/g. Thecorresponding CRYSTAF curve shows the tallest peak at 43.1° C. with apeak area of 56.8 percent. The delta between the DSC Tm and the Tcrystafis 72.9° C.

The DSC curve for the polymer of example 18 shows a peak with a 120.5°C. melting point (Tm) with a heat of fusion of 141.8 J/g. Thecorresponding CRYSTAF curve shows the tallest peak at 70.0° C. with apeak area of 94.0 percent. The delta between the DSC Tm and the Tcrystafis 50.5° C.

The DSC curve for the polymer of example 19 shows a peak with a 124.8°C. melting point (Tm) with a heat of fusion of 174.8 J/g. Thecorresponding CRYSTAF curve shows the tallest peak at 79.9° C. with apeak area of 87.9 percent. The delta between the DSC Tm and the Tcrystafis 45.0° C.

The DSC curve for the polymer of comparative D shows a peak with a 37.3°C. melting point (Tm) with a heat of fusion of 31.6 J/g. Thecorresponding CRYSTAF curve shows no peak equal to and above 30° C. Bothof these values are consistent with a resin that is low in density. Thedelta between the DSC Tm and the Tcrystaf is 7.3° C.

The DSC curve for the polymer of comparative E shows a peak with a124.0° C. melting point (Tm) with a heat of fusion of 179.3 J/g. Thecorresponding CRYSTAF curve shows the tallest peak at 79.3° C. with apeak area of 94.6 percent. Both of these values are consistent with aresin that is high in density. The delta between the DSC Tm and theTcrystaf is 44.6° C.

The DSC curve for the polymer of comparative F shows a peak with a124.8° C. melting point (Tm) with a heat of fusion of 90.4 J/g. Thecorresponding CRYSTAF curve shows the tallest peak at 77.6° C. with apeak area of 19.5 percent. The separation between the two peaks isconsistent with the presence of both a high crystalline and a lowcrystalline polymer. The delta between the DSC Tm and the Tcrystaf is47.2° C.

Physical Property Testing

Polymer samples are evaluated for physical properties such as hightemperature resistance properties, as evidenced by TMA temperaturetesting, pellet blocking strength, high temperature recovery, hightemperature compression set and storage modulus ratio, G′(25°C.)/G′(100° C.). Several commercially available polymers are included inthe tests: Comparative G* is a substantially linear ethylene/1-octenecopolymer (AFFINITY®, available from The Dow Chemical Company),Comparative H* is an elastomeric, substantially linear ethylene/1-octenecopolymer (AFFINITY®G8100, available from The Dow Chemical Company),Comparative I is a substantially linear ethylene/1-octene copolymer(AFFINITY®PL1840, available from The Dow Chemical Company), ComparativeJ is a hydrogenated styrene/butadiene/styrene triblock copolymer(KRATON™ G1652, available from KRATON Polymers), Comparative K is athermoplastic vulcanizate (TPV, a polyolefin blend containing dispersedtherein a crosslinked elastomer). Results are presented in Table 4.

TABLE 4 High Temperature Mechanical Properties 300% Pellet Strain TMA-1mm Blocking Recovery Compression penetration Strength G′(25° C.)/ (80°C.) Set (70° C.) Ex. (° C.) lb/ft² (kPa) G′(100° C.) (percent) (percent)D* 51 — 9 Failed — E* 130 — 18 — — F* 70 141 (6.8)  9 Failed 100  5 1040 (0)  6 81 49  6 110 — 5 — 52  7 113 — 4 84 43  8 111 — 4 Failed 41  997 — 4 — 66 10 108 — 5 81 55 11 100 — 8 — 68 12 88 — 8 — 79 13 95 — 6 8471 14 125 — 7 — — 15 96 — 5 — 58 16 113 — 4 — 42 17 108 0 (0)  4 82 4718 125 — 10 — — 19 133 — 9 — — G* 75 463 (22.2) 89 Failed 100 H* 70 213(10.2) 29 Failed 100 I* 111 — 11 — — J* 107 — 5 Failed 100 K* 152 — 3 —40

In Table 4, Comparative F (which is a physical blend of the two polymersresulting from simultaneous polymerizations using catalyst A1 and B1)has a 1 mm penetration temperature of about 70° C., while Examples 5-9have a 1 mm penetration temperature of 100° C. or greater. Further,examples 10-19 all have a 1 mm penetration temperature of greater than85° C., with most having 1 mm TMA temperature of greater than 90° C. oreven greater than 100° C. This shows that the novel polymers have betterdimensional stability at higher temperatures compared to a physicalblend. Comparative J (a commercial SEBS) has a good 1 mm TMA temperatureof about 107° C., but it has very poor (high temperature 70° C.)compression set of about 100 percent and it also failed to recover(sample broke) during a high temperature (80° C.) 300 percent strainrecovery. Thus the exemplified polymers have a unique combination ofproperties unavailable even in some commercially available, highperformance thermoplastic elastomers.

Similarly, Table 4 shows a low (good) storage modulus ratio, G'(25°C.)/G'(100° C.), for the inventive polymers of 6 or less, whereas aphysical blend (Comparative F) has a storage modulus ratio of 9 and arandom ethylene/octene copolymer (Comparative G) of similar density hasa storage modulus ratio an order of magnitude greater (89). It isdesirable that the storage modulus ratio of a polymer be as close to 1as possible. Such polymers will be relatively unaffected by temperature,and fabricated articles made from such polymers can be usefully employedover a broad temperature range. This feature of low storage modulusratio and temperature independence is particularly useful in elastomerapplications such as in pressure sensitive adhesive formulations.

The data in Table 4 also demonstrate that the polymers according toembodiments of the invention possess improved pellet blocking strength.In particular, Example 5 has a pellet blocking strength of 0 MPa,meaning it is free flowing under the conditions tested, compared toComparatives F and G which show considerable blocking. Blocking strengthis important since bulk shipment of polymers having large blockingstrengths can result in product clumping or sticking together uponstorage or shipping, resulting in poor handling properties.

High temperature (70° C.) compression set for the inventive polymers isgenerally good, meaning generally less than about 80 percent, preferablyless than about 70 percent and especially less than about 60 percent. Incontrast, Comparatives F, G, H and J all have a 70° C. compression setof 100 percent (the maximum possible value, indicating no recovery).Good high temperature compression set (low numerical values) isespecially needed for applications such as gaskets, window profiles,o-rings, and the like.

TABLE 5 Ambient Temperature Mechanical Properties Tensile 100% 300%Retractive Stress Abrasion: Notched Strain Strain Stress Com- Re- FlexTensile Tensile Elongation Tensile Elongation Volume Tear RecoveryRecovery at 150% pression laxation Modulus Modulus Strength at Break¹Strength at Break Loss Strength 21° C. 21° C. Strain Set 21° C. at 50%Ex. (MPa) (MPa) (MPa)¹ (%) (MPa) (%) (mm³) (mJ) (percent) (percent)(kPa) (Percent) Strain² D* 12 5 — — 10 1074 — — 91 83 760 — — E* 895 589— 31 1029 — — — — — — — F* 57 46 — — 12 824 93 339 78 65 400 42 —  5 3024 14 951 16 1116 48 — 87 74 790 14 33  6 33 29 — — 14 938 — — — 75 86113 —  7 44 37 15 846 14 854 39 — 82 73 810 20 —  8 41 35 13 785 14 81045 461 82 74 760 22 —  9 43 38 — — 12 823 — — — — — 25 — 10 23 23 — — 14902 — — 86 75 860 12 — 11 30 26 — — 16 1090 — 976 89 66 510 14 30 12 2017 12 961 13 931 — 1247  91 75 700 17 — 13 16 14 — — 13 814 — 691 91 — —21 — 14 212 160 — — 29 857 — — — — — — — 15 18 14 12 1127  10 1573 —2074  89 83 770 14 — 16 23 20 — — 12 968 — — 88 83 1040  13 — 17 20 18 —— 13 1252 — 1274  13 83 920  4 — 18 323 239 — — 30 808 — — — — — — — 19706 483 — — 36 871 — — — — — — — G* 15 15 — — 17 1000 — 746 86 53 110 2750 H* 16 15 — — 15 829 — 569 87 60 380 23 — I* 210 147 — — 29 697 — — —— — — — J* — — — — 32 609 — — 93 96 1900  25 — K* — — — — — — — — — — —30 — ¹Tested at 51 cm/minute ²measured at 38° C. for 12 hours

Table 5 shows results for mechanical properties for the new polymers aswell as for various comparison polymers at ambient temperatures. It maybe seen that the inventive polymers have very good abrasion resistancewhen tested according to ISO 4649, generally showing a volume loss ofless than about 90 mm³, preferably less than about 80 mm³, andespecially less than about 50 mm³. In this test, higher numbers indicatehigher volume loss and consequently lower abrasion resistance.

Tear strength as measured by tensile notched tear strength of theinventive polymers is generally 1000 mJ or higher, as shown in Table 5.Tear strength for the inventive polymers can be as high as 3000 mJ, oreven as high as 5000 mJ. Comparative polymers generally have tearstrengths no higher than 750 mJ.

Table 5 also shows that the polymers according to embodiments of theinvention have better retractive stress at 150 percent strain(demonstrated by higher retractive stress values) than some of thecomparative samples. Comparative Examples F, G and H have retractivestress value at 150 percent strain of 400 kPa or less, while theinventive polymers have retractive stress values at 150 percent strainof 500 kPa (Ex. 11) to as high as about 1100 kPa (Ex. 17). Polymershaving higher than 150 percent retractive stress values would be quiteuseful for elastic applications, such as elastic fibers and fabrics,especially nonwoven fabrics. Other applications include diaper, hygiene,and medical garment waistband applications, such as tabs and elasticbands.

Table 5 also shows that stress relaxation (at 50 percent strain) is alsoimproved (less) for the inventive polymers as compared to, for example,Comparative G. Lower stress relaxation means that the polymer retainsits force better in applications such as diapers and other garmentswhere retention of elastic properties over long time periods at bodytemperatures is desired.

Optical Testing

TABLE 6 Polymer Optical Properties Ex. Internal Haze (percent) Clarity(percent) 45° Gloss (percent) F* 84 22 49 G* 5 73 56  5 13 72 60  6 3369 53  7 28 57 59  8 20 65 62  9 61 38 49 10 15 73 67 11 13 69 67 12 875 72 13 7 74 69 14 59 15 62 15 11 74 66 16 39 70 65 17 29 73 66 18 6122 60 19 74 11 52 G* 5 73 56 H* 12 76 59 I* 20 75 59

The optical properties reported in Table 6 are based on compressionmolded films substantially lacking in orientation. Optical properties ofthe polymers may be varied over wide ranges, due to variation incrystallite size, resulting from variation in the quantity of chainshuttling agent employed in the polymerization.

Extractions of Multi-Block Copolymers

Extraction studies of the polymers of examples 5, 7 and Comparative Eare conducted. In the experiments, the polymer sample is weighed into aglass fritted extraction thimble and fitted into a Kumagawa typeextractor. The extractor with sample is purged with nitrogen, and a 500mL round bottom flask is charged with 350 mL of diethyl ether. The flaskis then fitted to the extractor. The ether is heated while beingstirred. Time is noted when the ether begins to condense into thethimble, and the extraction is allowed to proceed under nitrogen for 24hours. At this time, heating is stopped and the solution is allowed tocool. Any ether remaining in the extractor is returned to the flask. Theether in the flask is evaporated under vacuum at ambient temperature,and the resulting solids are purged dry with nitrogen. Any residue istransferred to a weighed bottle using successive washes of hexane. Thecombined hexane washes are then evaporated with another nitrogen purge,and the residue dried under vacuum overnight at 40° C. Any remainingether in the extractor is purged dry with nitrogen.

A second clean round bottom flask charged with 350 mL of hexane is thenconnected to the extractor. The hexane is heated to reflux with stirringand maintained at reflux for 24 hours after hexane is first noticedcondensing into the thimble. Heating is then stopped and the flask isallowed to cool. Any hexane remaining in the extractor is transferredback to the flask. The hexane is removed by evaporation under vacuum atambient temperature, and any residue remaining in the flask istransferred to a weighed bottle using successive hexane washes. Thehexane in the flask is evaporated by a nitrogen purge, and the residueis vacuum dried overnight at 40° C.

The polymer sample remaining in the thimble after the extractions istransferred from the thimble to a weighed bottle and vacuum driedovernight at 40° C. Results are contained in Table 7.

TABLE 7 ether ether C₈ hexane hexane C₈ residue wt. soluble soluble molesoluble soluble mole C₈ mole Sample (g) (g) (percent) percent¹ (g)(percent) percent¹ percent¹ Comp. 1.097 0.063 5.69 12.2 0.245 22.35 13.66.5 F* Ex. 5 1.006 0.041 4.08 — 0.040 3.98 14.2 11.6 Ex. 7 1.092 0.0171.59 13.3 0.012 1.10 11.7 9.9 ¹Determined by ¹³C NMR

Additional Polymer Examples 19A-J, Continuous Solution Polymerization,Catalyst A1/B2+DEZ Examples 19A-I

Continuous solution polymerizations are carried out in a computercontrolled well-mixed reactor. Purified mixed alkanes solvent (Isopar™ Eavailable from Exxon Mobil Chemical Company), ethylene, 1-octene, andhydrogen (where used) are combined and fed to a 27 gallon reactor. Thefeeds to the reactor are measured by mass-flow controllers. Thetemperature of the feed stream is controlled by use of a glycol cooledheat exchanger before entering the reactor. The catalyst componentsolutions are metered using pumps and mass flow meters. The reactor isrun liquid-full at approximately 550 psig pressure. Upon exiting thereactor, water and additive are injected in the polymer solution. Thewater hydrolyzes the catalysts, and terminates the polymerizationreactions. The post reactor solution is then heated in preparation for atwo-stage devolatization. The solvent and unreacted monomers are removedduring the devolatization process. The polymer melt is pumped to a diefor underwater pellet cutting.

Example 19J

Continuous solution polymerizations are carried out in a computercontrolled autoclave reactor equipped with an internal stirrer. Purifiedmixed alkanes solvent (Isopar™ E available from ExxonMobil ChemicalCompany), ethylene at 2.70 lbs/hour (1.22 kg/hour), 1-octene, andhydrogen (where used) are supplied to a 3.8 L reactor equipped with ajacket for temperature control and an internal thermocouple. The solventfeed to the reactor is measured by a mass-flow controller. A variablespeed diaphragm pump controls the solvent flow rate and pressure to thereactor. At the discharge of the pump, a side stream is taken to provideflush flows for the catalyst and cocatalyst injection lines and thereactor agitator. These flows are measured by Micro-Motion mass flowmeters and controlled by control valves or by the manual adjustment ofneedle valves. The remaining solvent is combined with 1-octene,ethylene, and hydrogen (where used) and fed to the reactor. A mass flowcontroller is used to deliver hydrogen to the reactor as needed. Thetemperature of the solvent/monomer solution is controlled by use of aheat exchanger before entering the reactor. This stream enters thebottom of the reactor. The catalyst component solutions are meteredusing pumps and mass flow meters and are combined with the catalystflush solvent and introduced into the bottom of the reactor. The reactoris run liquid-full at 500 psig (3.45 MPa) with vigorous stirring.Product is removed through exit lines at the top of the reactor. Allexit lines from the reactor are steam traced and insulated.Polymerization is stopped by the addition of a small amount of waterinto the exit line along with any stabilizers or other additives andpassing the mixture through a static mixer. The product stream is thenheated by passing through a heat exchanger before devolatilization. Thepolymer product is recovered by extrusion using a devolatilizingextruder and water cooled pelletizer.

Polymer Examples 20-23 were made using similar procedures as describedin the above. Process details and results are contained in Tables 8A-C.Selected polymer properties are provided in Tables 9A-B. Table 9C showsthe block indices for various polymers measured and calculated accordingthe methodology described above. For calculations performed herein,T_(A) is 372° K., P_(A) is 1.

TABLE 8A Polymerization Conditions for Polymers 19A-J Cat Cat Cat CatCocat [Zn]⁴ A1² A1 B2³ B2 DEZ DEZ 1 Cocat 1 Cocat 2 Cocat 2 in C₂H₄C₈H₁₆ Solv. H₂ T Conc. Flow Conc. Flow Conc Flow Conc. Flow Conc. Flowpolymer Ex. lb/hr lb/hr lb/hr sccm¹ ° C. ppm lb/hr ppm lb/hr wt % lb/hrppm lb/hr ppm lb/hr ppm 19A 55.29 32.03 323.03 101 120 600 0.25 200 0.423.0 0.70 4500 0.65 525 0.33 248 19B 53.95 28.96 325.3 577 120 600 0.25200 0.55 3.0 0.24 4500 0.63 525 0.11 90 19C 55.53 30.97 324.37 550 120600 0.216 200 0.609 3.0 0.69 4500 0.61 525 0.33 246 19D 54.83 30.58326.33 60 120 600 0.22 200 0.63 3.0 1.39 4500 0.66 525 0.66 491 19E54.95 31.73 326.75 251 120 600 0.21 200 0.61 3.0 1.04 4500 0.64 525 0.49368 19F 50.43 34.80 330.33 124 120 600 0.20 200 0.60 3.0 0.74 4500 0.52525 0.35 257 19G 50.25 33.08 325.61 188 120 600 0.19 200 0.59 3.0 0.544500 0.51 525 0.16 194 19H 50.15 34.87 318.17 58 120 600 0.21 200 0.663.0 0.70 4500 0.52 525 0.70 259 19I 55.02 34.02 323.59 53 120 600 0.44200 0.74 3.0 1.72 4500 0.70 525 1.65 600 19J 7.46 9.04 50.6 47 120 1500.22 76.7 0.36 0.5 0.19 — — — — — ¹standard cm³/min²[N-(2,6-di(1-methylethyl)phenyl)amido)(2-isopropylphenyl)(α-naphthalen-2-diyl(6-pyridin-2-diyl)methane)]hafniumdimethyl³bis-(1-(2-methylcyclohexyl)ethyl)(2-oxoyl-3,5-di(t-butyl)phenyl)immino)zirconium dimethyl ⁴ppm in final product calculated by mass balance

TABLE 8B Additional Polymerization Conditions for Polymers 19A-J PolyRate⁵ Conv⁶ Polymer [Zn]/[C₂H₄] * Ex. lb/hr wt % wt % [C₂H₄]/[Zn]⁷ 1000⁸Eff.⁹ 19A 83.94 88.0 17.28 775 1.29 297 19B 80.72 88.1 17.2 2222 0.45295 19C 84.13 88.9 17.16 775 1.29 293 19D 82.56 88.1 17.07 395 2.53 28019E 84.11 88.4 17.43 513 1.95 288 19F 85.31 87.5 17.09 725 1.38 319 19G83.72 87.5 17.34 1000 1.0 333 19H 83.21 88.0 17.46 752 1.33 312 19I86.63 88.0 17.6 317 3.15 275 19J — — — 1786 0.56 — ⁵polymer productionrate ⁶weight percent ethylene conversion in reactor ⁷molar ratio inreactor; Zn/C₂ * 1000 = (Zn feed flow * Zn concentration/1000000/Mw ofZn)/(Total Ethylene feed flow * (1 − fractional ethylene conversionrate)/Mw of Ethylene) * 1000. Please note that “Zn” in “Zn/C₂ * 1000”refers to the amount of zinc in diethyl zinc (“DEZ”) used in thepolymerization process, and “C2” refers to the amount of ethylene usedin the polymerization process. ⁸molar ratio in reactor ⁹efficiency, lbpolymer/lb M where lb M = lb Hf + lb Z

TABLE 8C Polymerization Conditions for Polymers 20-23. Cat Cat A1 CatCat B2 DEZ Co.* Co.* Solv. H₂ T A1² Flow B2³ Flow Conc. Ex. Type kg/hrkg/hr sccm¹ ° C. ppm kg/hr ppm Kg/hr ppm Zn 20 Octene 1.6 11.4 104.8 11971.7 0.059 46.4 0.055 1688 21 Butene 1.6 10.5 9.9 120 94.2 0.065 10.50.100 9222 22 Butene 1.6 10.5 37.5 120 94.2 0.064 10.5 0.088 9222 23Propylene 1.4 9.8 4.9 120 53.1 0.024 58.1 0.098 3030 DEZ Cocat Cocat[Zn]/ Poly Flow Conc. Flow [C₂H₄]/ [C₂H₄] * Rate⁶ Conv⁷ Solids Ex. kg/hrppm kg/hr [Zn]⁴ 1000⁵ kg/hr % % Eff.⁸ 20 0.018 1743 0.118 9166 0.11 1.690 11.4 239 21 0.068 1168 0.057 442 2.26 1.7 90.5 12.2 235 22 0.018 11680.054 1851 0.54 1.6 90 11.9 228 23 0.151 429.4 0.139 1030 0.97 1.1 82.59.4 184 *“Co.” stands for “comonomer”. ¹standard cm3/min²[N-(2,6-di(1-methylethyl)phenyl)amido)(2-isopropylphenyl)(α-napthalen-2-diyl(6-pyridin-2-diyl)methane)]hafniumdimethyl³bis-(1-(2-methylcyclohexyl)ethyl)(2-oxoyl-3,5-di(t-butyl)phenyl)immino)zirconium dibenzyl ⁴molar ratio in reactor; Zn/C₂ * 1000 = (Zn feedflow * Zn concentration/1000000/Mw of Zn)/(Total Ethylene feed flow * (1− fractional ethylene conversion rate)/Mw of Ethylene) * 1000. Pleasenote that “Zn” in “Zn/C₂ * 1000” refers to the amount of zinc in diethylzinc (“DEZ”) used in the polymerization process, and “C2” refers to theamount of ethylene used in the polymerization process. ⁵molar ratio inreactor ⁶polymer production rate ⁷percent ethylene conversion in reactor⁸efficiency, kg polymer/g M where g M = g Hf + g Zr

TABLE 9A Polymer Physical Properties Density Mw Mn Heat of Tm TcTCRYSTAF Tm − TCRYSTAF CRYSTAF Peak Ex. (g/cc) I₂ I₁₀ I₁₀/I₂ (g/mol)(g/mol) Mw/Mn Fusion (J/g) (° C.) (° C.) (° C.) (° C.) Area (wt %) 19A0.8781 0.9 6.4 6.9 123700 61000 2.0 56 119 97 46 73 40 19B 0.8749 0.97.3 7.8 133000 44300 3.0 52 122 100 30 92 76 19C 0.8753 5.6 38.5 6.981700 37300 2.2 46 122 100 30 92 8 19D 0.8770 4.7 31.5 6.7 80700 397002.0 52 119 97 48 72 5 19E 0.8750 4.9 33.5 6.8 81800 41700 2.0 49 121 9736 84 12 19F 0.8652 1.1 7.5 6.8 124900 60700 2.1 27 119 88 30 89 89 19G0.8649 0.9 6.4 7.1 135000 64800 2.1 26 120 92 30 90 90 19H 0.8654 1.07.0 7.1 131600 66900 2.0 26 118 88 — — — 19I 0.8774 11.2 75.2 6.7 6640033700 2.0 49 119 99 40 79 13 19J 0.8995 5.6 39.4 7.0 75500 29900 2.5 101122 106 — — —

TABLE 9B Polymer Physical Properties of Compression Molded FilmsImmediate Immediate Immediate Set after Set after Set after Melt 100%300% 500% Recovery after Recovery after Recovery after Density IndexStrain Strain Strain 100% 300% 500% Example (g/cm³) (g/10 min) (%) (%)(%) (%) (%) (%) 19A 0.878 0.9 15 63 131 85 79 74 19B 0.877 0.88 14 49 9786 84 81 19F 0.865 1 — — 70 — 87 86 19G 0.865 0.9 — — 66 — — 87 19H0.865 0.92 — 39 — — 87 —

TABLE 9C Block Index for Selected Polymers Average Block Index (“BI”)Second Moment About the Mean Density I₂ Weight Weight Average ExampleComonomer (g/cc) g/10 min. Zn/C₂H₄ * 1000 Average BI BI F* Octene 0.88950.9 0 0 0 L* Octene 0.905 0.8 — 0 0.01 M* Octene 0.902 1.0 — 0 0 20Octene 0.8841 1.0 0.11 0.2 0.45  8 Octene 0.8828 0.9 0.56 0.59 0.32 19AOctene 0.8781 0.9 1.3 0.62 0.17  5 Octene 0.8786 1.5 2.4 0.53 0.136 19BOctene 0.8749 0.9 0.45 0.54 0.35 19I Octene 0.8774 11.2 3.15 0.59 0.2221 Butene 0.8795 0.9 1.89 0.65 0.22 22 Butene 0.8802 1.1 1.71 0.66 0.3323 Propylene 0.883 1.2 0.97 0.61 0.24 1) L* is a ultra low densitypolyethylene made by Zieglar-Natta catalysis and available from The DowChemical Company under the trademark of ATTANE ™ 4203. 2) M* is apolyethylene copolymer made by constrained geometry catalysis (i.e.,single-site catalyst) and available from The Dow Chemical Company underthe trademark of AFFINITY ® PL1880G.

As shown in Table 9C, all the inventive polymers have a weight averageblock index of greater than zero, whereas the random copolymers(Polymers F*, L*, and M*) all have a block index of zero orsubstantially zero (such as 0.01).

FIG. 10 shows the block index distribution for Polymer F*, Polymer 20,Polymer 8, and Polymer 5 as a function of the ATREF temperature. ForPolymer F*, the block index for all the ATREF fraction is zero orsubstantially zero (i.e., ≦0.01). Polymer 20 was made with a relativelylow level of the shuttling agent, diethyl zinc (“DEZ”). While the weightaverage block index for the whole polymer is about 0.2, the polymerincludes four fractions with a block index from about 0.7 to about 0.9.For Polymers 5 and 8, their weight average block indices are notdrastically different (0.52 vs. 0.59), considering the DEZ level isabout a four-fold difference. Moreover, most of their fractions have ablock index of about 0.6 or higher. Similar results are seen betweenPolymer 5 and Polymer 19B, which is illustrated in FIG. 11. However,there are some notable differences in the block index for the fractionswhich elute from about 70° C. to about 90° C. Polymer 19B was made witha higher level (about four fold higher) of DEZ than Polymer 5. However,Polymer 5 has more fractions that have higher block indices. This seemsto suggest that there might be an optimal DEZ level for making fractionswith higher block indices (i.e., greater than about 0.6).

The effect of the DEZ concentration level on the average block index forsome of the polymers in Table 9C is illustrated in FIG. 12. The plotsseem to suggest that the average block index increases with increasingDEZ initially. Once Zn/C₂H₄*1000 exceeds about 0.5, the average blockindex appears to level off and may even drop off if too much DEZ isused.

FIG. 13 is a plot of the square root of the second moment about the meanweight average block index as a function of [Zn/C₂H₄]*1000. It appearsto decrease as DEZ increases. This would indicated that the distributionof the block indices of the fractions are becoming narrower (i.e., morehomogeneous).

TREF and NMR Data

Tables 10-14 list TREF, DSC, IR, and NMR data for Polymers 5, 8, 14, and19 and various comparative polymers.

TABLE 10 TREF Fractions from Ziegler-Natta LLDPE Ex. L * - Ziegler-NattaExample (Attane ™ 4203, 0.90 g/cm³, 0.8 I₂) Mol % DeltaH FractionationATREF T Octene Tm melt Temperature (° C.) (NMR) (° C.) (J/g) 35-40 498.0 82 84 40-45 56.5 7.0 86 97 45-50 57.5 6.6 89 101 50-55 61 6.0 92 9655-60 63.5 5.4 95 99 60-65 67.5 4.9 98 104 65-70 72 4.3 101 112 70-7575.5 3.7 104 112 75-80 79 3.1 107 122 80-85 83.5 2.5 112 131 85-90 901.7 116 154 90-95 95.5 1.1 123 160  95-100 100 0.5 128 185 100-105 1010.2 130 195

TABLE 11 TREF Fractions from Random Copolymer Ex. M* - Random CopolymerExample (AFFINITY ® PL1880, 0.90 g/cm³, 1 I₂) Mol % DeltaH FractionationATREF T Octene Tm melt Temperature (° C.) (NMR) (° C.) (J/g) 35-40 51.5NM 83 102 40-45 56 7.3 87 96 45-50 61.5 6.5 90 101 50-55 63.5 5.7 93 10055-60 66.5 5.3 95 104 60-65 69.5 4.9 97 105 65-70 72 4.4 99 111 70-75 744.2 101 111 75-80 76.5 3.8 106 112

TABLE 12 TREF Fractions from Inventive Example 5 Inventive Example 5 Mol% DeltaH Fractionation ATREF T Octene melt Temperature (° C.) (NMR) Tm(° C.) (J/g) 60-65 70.5 12.6 106 45 65-70 73 12.2 108 48 70-75 77 11.7111 51 75-80 81 10.5 113 57 80-85 84 9.8 115 68 85-90 88.5 7.0 119 8390-95 92 5.2 123 110

TABLE 13 TREF Fractions from Inventive Example 8 Inventive Example 8 Mol% DeltaH Fractionation ATREF T Octene melt Temperature (° C.) (NMR) Tm(° C.) (J/g) 50-55 20 16.5 98 28 55-60 57.5 16.2 104 29 60-65 61.5 16.5106 28 65-70 65.5 16.2 109 29 70-75 70.5 15.7 112 31 75-80 73 15.5 11432 80-85 81.5 11.6 117 37 85-90 89.5 10.7 120 58 90-95 96 4.6 126 125 95-100 96.5 1.5 129 180

TABLE 14 ATREF Peak comonomer composition for random copolymers andexamples 5, 8, 14, 19 Mol % Infra-red Octene Infra-red Infra-red FWHMMol % TREF FWHM FWHM CH3/CH2 Density Octene T_(ATREF) Peak CH2 CH3 AreaExample (g/cc) I2 (NMR) (° C.) (Infra-red) Area Area Ratio N* 0.96 1.0 0102 0.0 37.5 28.2 0.753 O* 0.9371 2.0 0.69 95 1.2 29.0 22.2 0.765 M*0.9112 1.0 3.88 79 4.0 77.5 61.0 0.786 P* 0.9026 1.1 5.57 70 5.1 74.359.0 0.794 Q* 0.8872 0.9 9.06 57 9.2 30.9 25.5 0.824 Ex. 5 0.8786 1.5 NA82 11.4 77.5 61.0 0.841 Ex. 8 0.8828 0.9 NA 90 12.2 34.0 28.8 0.846 Ex.14 0.9116 2.6 NA 92 6.5 23.4 18.8 0.805 Ex. 19 0.9344 3.4 NA 97 2.8 25.319.7 0.777 Infra-red detector calibration: Mol % Octene = 133.38 (FWHMCH₃/CH₂ Area) − 100.8 N* is an ethylene homopolymer. O* is anethylene/octene copolymer available from The Dow Chemical Company underAFFINITY ® HF1030. P* is an ethylene/octene copolymer available from TheDow Chemical Company under AFFINITY ® PL1880. Q* is an ethylene/octenecopolymer available from The Dow Chemical Company under AFFINITY ®VP8770.

Calculation of Block Index

With reference to FIGS. 8-9, the calculation of block indices isexemplified for Polymer 5. In the calculations, the followingcalibration equation is used:

LnP=−237.8341/T _(ATREF)+0.6390

where P is the ethylene mole fraction, and T_(ATREF) is the ATREFelution temperature. In addition, the following parameters are used:

Parameter Value Explanation T_(A) 372.15 Analytical TREF elutiontemperature (° K) of hard segment P_(A) 1.000 Mole fraction of ethyleneof hard segment P_(AB) 0.892 Mole fraction of ethylene of whole polymerT_(AB) 315.722 Calculated equivalent analytical TREF elution temperature(° K) of whole polymer from whole polymer ethylene content

Table 15 gives details of the calculations for Polymer 5. The weightedaverage block index, ABI, for Polymer 5, is 0.531, and the square rootof sum of weighted squared deviations about the weighted mean is 0.136.The partial sum of weights with fraction BI greater than zero (see note2 below) is 0.835.

TABLE 15 Fractional Block Index (BI) Calculations Random EquivalentATREF Random Weighted Temperature Equivalent Squared from moleFractional Fractional Deviations NMR fraction Block Block Index aboutATREF Mole Ethylene ethylene Index based on Weighted the ElutionFraction Weight Weight from based on Log_(e) of mole Fractional WeightedTemperature Ethylene Fraction Fraction ATREF Temperature fraction BlockMean Weight (° K) (NMR) Recovered (° K) Temperature formula formulaIndices (Note 2) Recovered Array Variable Name Fraction # (g) T_(x)P_(x) W_(i) T_(X0) P_(X0) BI_(i) BI_(i) W_(i) * BI_(i) W_(i) * (BI_(i) −ABI) 1 3.0402 (Note 1) 0.859 0.165 (Note 1) (Note 1) 0 0 0 (Note 1) 21.9435 340 0.873 0.106 307 0.941 0.659 0.659 0.070 0.0017 3 0.7455 343.50.883 0.041 312 0.948 0.622 0.622 0.025 0.0003 4 1.0018 346 0.882 0.054311 0.953 0.676 0.676 0.037 0.0011 5 2.3641 350 0.896 0.128 318 0.9600.607 0.607 0.078 0.0007 6 4.1382 354 0.895 0.225 317 0.968 0.684 0.6840.154 0.0052 7 3.5981 357 0.902 0.195 320 0.973 0.665 0.665 0.130 0.00358 1.2280 361.5 0.930 0.067 334 0.981 0.470 0.470 0.031 0.0003 9 0.3639365 0.948 0.020 343 0.987 0.357 0.357 0.007 0.0006 ABI 18.4233 TotalWeight 1.000 Normalization check Weighted Sums 0.531 0.0135 (Note 1):Fraction #1 does not crystallize in the analytical ATREF and is assignedBI_(i) = 0 (Note 2): The weighted squared deviations about the weightedmean use only BI_(i) > 0

Measurement of Weight Percent of Hard and Soft Segments

As discussed above, the block interpolymers comprise hard segments andsoft segments. The soft segments can be present in a block interpolymerfrom about 1 weight percent to about 99 weight percent of the totalweight of the block interpolymer, preferably from about 5 weight percentto about 95 weight percent, from about 10 weight percent to about 90weight percent, from about 15 weight percent to about 85 weight percent,from about 20 weight percent to about 80 weight percent, from about 25weight percent to about 75 weight percent, from about 30 weight percentto about 70 weight percent, from about 35 weight percent to about 65weight percent, from about 40 weight percent to about 60 weight percent,or from about 45 weight percent to about 55 weight percent. Conversely,the hard segments can be present in a similar range as above. The softsegment weight percentage (and thus the hard segment weight percentage)can be measured by DSC or NMR.

Hard Segment Weight fraction Measured by DSC

For a block polymer having hard segments and soft segments, the densityof the overall block polymer, ρ_(overall), satisfies the followingrelationship:

$\frac{1}{\rho_{overall}} = {\frac{x_{hard}}{\rho_{hard}} + \frac{x_{soft}}{\rho_{soft}}}$

where ρh_(hard), and ρ_(soft), are the theoretical density of the hardsegments and soft segments, respectively.χ_(hard), and χ_(soft), are theweight fraction of the hard segments and soft segments, respectively andthey add up to one. Assuming ρ_(hard) is equal to the density ofethylene homopolymer, i.e., 0.96 g/cc, and transposing the aboveequation, one obtains the following equation for the weight fraction ofhard segments:

$x_{h} = \frac{\frac{1}{\rho_{Overall}} - \frac{1}{\rho_{Soft}}}{{- \frac{1}{\rho_{Overall}}} + \frac{1}{0.96\mspace{14mu} g\text{/}{cc}}}$

In the above equation, ρ_(overall) can be measured from the blockpolymer. Therefore, if ρ_(soft) is known, the hard segment weightfraction can be calculated accordingly. Generally, the soft segmentdensity has a linear relationship with the soft segment meltingtemperature, which can be measured by DSC over a certain range:

ρ_(soft) =A*T _(m) +B

where A and B are constants, and T_(m), is the soft segment meltingtemperature in degrees Celsius. A and B can be determined by running DSCon various copolymers with a known density to obtain a calibrationcurve. It is preferable to create a soft segment calibration curve thatspan the range of composition (both comonomer type and content) presentin the block copolymer. In some embodiments, the calibration curvesatisfies the following relationship:

ρ_(soft)=0.00049*T _(m)+0.84990

Therefore, the above equation can be used to calculate the soft segmentdensity if T_(m) in degrees Celsius is known.

For some block copolymers, there is an identifiable peak in DSC that isassociated with the melting of the soft segments. In this case, it isrelatively straightforward to determine T_(m) for the soft segments.Once T_(m), in degrees Celsius is determined from DSC, the soft segmentdensity can be calculated and thus the hard segment weight fraction.

For other block copolymers, the peak associated with the melting of thesoft segments is either a small hump (or bump) over the baseline orsometimes not visible as illustrated in FIG. 14. This difficulty can beovercome by converting a normal DSC profile into a weighted DSC profileas shown in FIG. 15. The following method is used to convert a normalDSC profile to a weighted DSC profile.

In DSC, the heat flow depends on the amount of the material melting at acertain temperature as well as on the temperature-dependent specificheat capacity. The temperature-dependence of the specific heat capacityin the melting regime of linear low density polyethylene leads to anincrease in the heat of fusion with decreasing comonomer content. Thatis, the heat of fusion values get progressively lower as thecrystallalinity is reduced with increasing comonomer content. See Wild,L. Chang, S.; Shankernarayanan, M J. Improved method for compositionalanalysis of polyolefins by DSC. Polym. Prep 1990; 31: 270-1, which isincorporated by reference herein in its entirety.

For a given point in the DSC curve (defined by its heat flow in wattsper gram and temperature in degrees Celsius), by taking the ratio of theheat of fusion expected for a linear copolymer to thetemperature-dependent heat of fusion (ΔH(T)), the DSC curve can beconverted into a weight-dependent distribution curve.

The temperature-dependent heat of fusion curve can be calculated fromthe summation of the integrated heat flow between two consecutive datapoints and then represented overall by the cumulative enthalpy curve.

The expected relationship between the heat of fusion for linearethylene/octene copolymers at a given temperature is shown by the heatof fusion versus melting temperature curve. Using random ethylene/octenecopolymers, one can obtain the following relationship:

Melt Enthalpy (J/g)=0.0072*T _(m) ²(° C.)+0.3138*T _(m)(° C.)+8.9767

For each integrated data point, at a given temperature, by taking aratio of the enthalpy from the cumulative enthalpy curve to the expectedheat of fusion for linear copolymers at that temperature, fractionalweights can be assigned to each point of the DSC curve.

It should be noted that, in the above method, the weighted DSC iscalculated in the range from 0° C. until the end of melting. The methodis applicable to ethylene/octene copolymers but can be adapted to otherpolymers.

Applying the above methodology to various polymers, the weightpercentage of the hard segments and soft segments were calculated, whichare listed in Table 16. It should be noted that sometimes it isdesirable to assign 0.94 g/cc to the theoretical hard segment density,instead of using the density for homopolyethylene, due to the fact thatthe hard segments may include a small amount of comonomers.

TABLE 16 Calculated Weight Percentage of Hard and Soft Segments forVarious Polymers Soft Segment Calculated Polymer T_(m) (° C.) from SoftCalculated Calculated Example Overall weighted Segment wt % Hard wt %Soft No. Density DSC Density Segment Segment F* 0.8895 20.3 0.860 32%68%  5 0.8786 13.8 0.857 23% 77%  6 0.8785 13.5 0.857 23% 77%  7 0.882516.5 0.858 26% 74%  8 0.8828 17.3 0.858 26% 74%  9 0.8836 17.0 0.858 27%73% 10 0.878 15.0 0.857 22% 78% 11 0.882 16.5 0.858 25% 75% 12 0.87019.5 0.859 12% 88% 13 0.872 23.0 0.861 12% 88% 14 0.912 21.8 0.861 54%46% 15 0.8719 0.5 0.850 22% 78% 16 0.8758 0.3 0.850 26% 74% 18 0.9192 —— — — 19 0.9344 38.0 0.869 74% 26% 17 0.8757 2.8 0.851 25% 75% 19A0.8777 11.5 0.856 23% 77% 19B 0.8772 14.3 0.857 22% 78% 19J 0.8995 4.80.852 47% 53%

Hard Segment Weight Percentage Measured by NMR

¹³C NMR spectroscopy is one of a number of techniques known in the artfor measuring comonomer incorporation into a polymer. An example of thistechnique is described for the determination of comonomer content forethylene/α-olefin copolymers in Randall (Journal of MacromolecularScience, Reviews in Macromolecular Chemistry and Physics, C29 (2 & 3),201-317 (1989)), which is incorporated by reference herein in itsentirety. The basic procedure for determining the comonomer content ofan ethylene/olefin interpolymer involves obtaining a ¹³C NMR spectrumunder conditions where the intensity of the peaks corresponding to thedifferent carbons in a sample is directly proportional to the totalnumber of contributing nuclei in the sample. Methods for ensuring thisproportionality are known in the art and involve allowance forsufficient time for relaxation after a pulse, the use ofgated-decoupling techniques, relaxation agents, and the like. Therelative intensity of a peak or group of peaks is obtained in practicefrom its computer-generated integral. After obtaining the spectrum andintegrating the peaks, those peaks associated with the comonomer areassigned. This assignment can be made by reference to known spectra orliterature, or by synthesis and analysis of model compounds, or by theuse of isotopically labeled comonomers. The mole % comonomer can bedetermined by the ratio of the integrals corresponding to the number ofmoles of comonomer to the integrals corresponding to the number of molesof all of the monomers in the interpolymer, as described in theaforementioned Randall reference.

Since the hard segment generally has less than about 2.0 wt % comonomer,its major contribution to the spectrum is only for the integral at about30 ppm. The hard segment contribution to the peaks not at 30 ppm isassumed negligible at the start of the analysis. So for the startingpoint, the integrals of the peaks not at 30 ppm are assumed to come fromthe soft segment only. These integrals are fit to a first orderMarkovian statistical model for copolymers using a linear least squaresminimization, thus generating fitting parameters (i.e., probability ofoctene insertion after octene, P_(oo), and probability of octeneinsertion after ethylene, P_(eo)) that are used to compute the softsegment contribution to the 30 ppm peak. The difference between thetotal measured 30 ppm peak integral and the computed soft segmentintegral contribution to the 30 ppm peak is the contribution from thehard segment. Therefore, the experimental spectrum has now beendeconvoluted into two integral lists describing the soft segment andhard segment, respectively. The calculation of weight percentage of thehard segment is straight forward and calculated by the ratio of the sumof integrals for the hard segment spectrum to the sum of integrals forthe overall spectrum.

From the deconvoluted soft segment integral list, the comonomercomposition can be calculated according to the method of Randall, forexample. From the comonomer composition of the overall spectrum and thecomonomer composition of the soft segment, one can use mass balance tocompute the comonomer composition of the hard segment. From thecomonomer composition of the hard segment, Bernoullian statistics isused to calculate the contribution of the hard segment to the integralsof non 30 ppm peaks. There is usually so little octene, typically fromabout 0 to about 1 mol %, in the hard segment that Bernoullianstatistics is a valid and robust approximation. These contributions arethen subtracted out from the experimental integrals of the non 30 ppmpeaks. The resulting non 30 ppm peak integrals are then fitted to afirst order Markovian statistics model for copolymers as described inthe above paragraph. The iterative process is performed in the followingmanner: fit total non 30 ppm peaks then compute soft segmentcontribution to 30 ppm peak; then compute soft/hard segment split andthen compute hard segment contribution to non 30 ppm peaks; then correctfor hard segment contribution to non 30 ppm peaks and fit resulting non30 ppm peaks. This is repeated until the values for soft/hard segmentsplit converge to a minimum error function. The final comonomercompositions for each segment are reported.

Validation of the measurement is accomplished through the analysis ofseveral in situ polymer blends. By design of the polymerization andcatalyst concentrations the expected split is compared to the measuredNMR split values. The soft/hard catalyst concentration is prescribed tobe 74%/26%. The measured value of the soft/hard segment split is78%/22%. Table 17 shows the chemical shift assignments for ethyleneoctene polymers.

TABLE 17 Chemical Shift Assignments for Ethylene/Octene Copolymers.  41-40.6 ppm OOOE/EOOO αα CH2 40.5-40.0 ppm EOOE αα CH2 38.9-37.9 ppmEOE CH 36.2-35.7 ppm OOE center CH 35.6-34.7 ppm OEO αγ, OOO center 6B,OOEE αδ+, OOE center 6B CH2 34.7-34.1 ppm EOE αδ+, EOE 6B CH2 33.9-33.5ppm OOO center CH 32.5-32.1 ppm 3B CH2 31.5-30.8 ppm OEEO γγ CH230.8-30.3 ppm OE γδ+ CH2 30.3-29.0 ppm 4B, EEE δ+δ+ CH2 28.0-26.5 ppm OEβδ+ 5B 25.1-23.9 ppm OEO ββ 23.0-22.6 ppm 2B 14.5-14.0 ppm 1B

The following experimental procedures are used. A sample is prepared byadding 0.25 g in a 10 mm NMR tube with 2.5 mL of stock solvent. Thestock solvent is made by dissolving 1 g perdeuterated1,4-dichlorobenzene in 30 mL ortho-dichlorobenzene with 0.025 M chromiumacetylacetonate (relaxation agent). The headspace of the tube is purgedof oxygen by displacement with pure nitrogen. The sample tube is thenheated in a heating block set at 150° C. The sample tube is repeatedlyvortexed and heated until the solution flows consistently from top ofthe solution column to the bottom. The sample tube is then left in theheat block for at least 24 hours to achieve optimum sample homogeneity.

The ¹³C NMR data is collected using a Varian Inova Unity 400 MHz systemwith probe temperature set at 125° C. The center of the excitationbandwidth is set at 32.5 ppm with spectrum width set at 250 ppm.Acquisition parameters are optimized for quantitation including 90°pulse, inverse gated ¹H decoupling, 1.3 second acquisition time, 6seconds delay time, and 8192 scans for data averaging. The magneticfield is carefully shimmed to generate a line shape of less than 1 Hz atfull width half maximum for the solvent peaks prior to data acquisition.The raw data file is processed using NUTS processing software (availablefrom Acorn NMR, Inc. in Livermore, Calif.) and a list of integrals isgenerated.

Inventive Polymer 19A is analyzed for the soft/hard segment split andsoft/hard comonomer composition. The following is the list of integralsfor this polymer. The NMR spectrum for Polymer 19A is shown in FIG. 16.

Integral limit Integral value 41.0-40.6 ppm 1.067 40.5-40.0 ppm 6.24738.9-37.9 ppm 82.343 36.2-35.7 ppm 14.775 35.6-34.7 ppm 65.563 34.7-34.1ppm 215.518 33.9-33.5 ppm 0.807 32.5-32.1 ppm 99.612 31.5-30.8 ppm14.691 30.8-30.3 ppm 115.246 30.3-29.0 ppm 1177.893 28.0-26.5 ppm258.294 25.1-23.9 ppm 19.707 23.0-22.6 ppm 100 14.5-14.0 ppm 99.895

Using Randall's triad method, the total octene weight percentage in thissample is determined to be 34.6%. Using all the above integralsexcluding the 30.3-29.0 ppm integral to fit a first order Markovianstatistical model, the values for Poo and Peo are determined to be0.08389 and 0.2051, respectively. Using these two parameters, thecalculated integral contribution from the soft segment to the 30 ppmpeak is 602.586. Subtraction of 602.586 from the observed total integralfor the 30 ppm peak, 1177.893, yields the contribution of the hardsegment to the 30 ppm peak of 576.307. Using 576.307 as the integral forthe hard segment, the weight percentage of hard segment is determined tobe 26%. Therefore the soft segment weight percentage is 100−26=74%.Using the above values for P_(oo) and P_(eo), the octene weightpercentage of the soft segment is determined to be 47%. Using theoverall octene weight percentage and the octene weight percentage of thesoft segment as well as the soft segment weight percentage, the octeneweight percentage in the hard segment is calculated to be negative 2 wt%. This value is within the error of the measurement. Thus there is noneed to iterate back to account for hard segment contribution to non 30ppm peaks. Table 18 summarizes the calculation results for Polymers 19A,B, F and G.

TABLE 18 Hard and Soft Segments Data for Polymers 19A, B, F and G wt %wt % octene in wt % Soft Hard Soft Example Segment Segment Segment 19A74 26 47 19B 74 26 48 19F 86 14 49 19G 84 16 49

As demonstrated above, embodiments of the invention provide a new classof ethylene and α-olefin block interpolymers. The block interpolymersare characterized by an average block index of greater than zero,preferably greater than 0.2. Due to the block structures, the blockinterpolymers have a unique combination of properties or characteristicsnot seen for other ethylene/α-olefin copolymers. Moreover, the blockinterpolymers comprise various fractions with different block indices.The distribution of such block indices has an impact on the overallphysical properties of the block interpolymers. It is possible to changethe distribution of the block indices by adjusting the polymerizationconditions, thereby affording the abilities to tailor the desiredpolymers. Such block interpolymers have many end-use applications. Forexample, the block interpolymers can be used to make polymer blends,fibers, films, molded articles, lubricants, base oils, etc. Otheradvantages and characteristics are apparent to those skilled in the art.

While the invention has been described with respect to a limited numberof embodiments, the specific features of one embodiment should not beattributed to other embodiments of the invention. No single embodimentis representative of all aspects of the invention. In some embodiments,the compositions or methods may include numerous compounds or steps notmentioned herein. In other embodiments, the compositions or methods donot include, or are substantially free of, any compounds or steps notenumerated herein. Variations and modifications from the describedembodiments exist. The method of making the resins is described ascomprising a number of acts or steps. These steps or acts may bepracticed in any sequence or order unless otherwise indicated. Finally,any number disclosed herein should be construed to mean approximate,regardless of whether the word “about” or “approximately” is used indescribing the number. The appended claims intend to cover all thosemodifications and variations as falling within the scope of theinvention.

1. An ethylene/α-olefin interpolymer comprising polymerized units ofethylene and α-olefin, wherein the interpolymer is a block interpolymercomprising at least about 60 mole percent ethylene and wherein the blockinterpolymer is characterized by an average block index greater thanabout 0.1 and up to about 1.0, a molecular weight distribution,M_(w)/M_(n), greater than about 1.3; and wherein the ethylene/α-olefininterpolymer has one or more of the following characteristics: (a) ahexane soluble portion comprising polymerized units of ethylene andα-olefin; (b) a polydispersity index fitting a Schultz-Florydistribution; or (c) a formula (AB)n where n is at least 1, “A”represents a block of polymerized units in which ethylene is present inan amount greater than 95 weight percent, and “B” represents a block ofpolymerized units in which α-olefin is present in an amount greater than5 weight percent wherein each of block A and B has monomers randomlydistributed within the block.
 2. The ethylene/α-olefin interpolymer ofclaim 1 wherein the average block index is greater than about 0.1 butless than about 0.4.
 3. The ethylene/α-olefin interpolymer of claim 1,wherein the average block index is in the range from about 0.1 to about0.3.
 4. The ethylene/α-olefin interpolymer of claim 1, wherein theaverage block index is in the range from about 0.4 to about 1.0.
 5. Theethylene/α-olefin interpolymer of claim 1, wherein the average blockindex is in the range from about 0.3 to about 0.7.
 6. Theethylene/α-olefin interpolymer of claim 1, wherein the average blockindex is in the range from about 0.6 to about 0.9.
 7. Theethylene/α-olefin interpolymer of claim 1, wherein the average blockindex is in the range from about 0.5 to about 0.7.
 8. Theethylene/α-olefin interpolymer of claim 1, wherein the ethylene/α-olefininterpolymer has a hexane soluble portion comprising polymerized unitsof ethylene and α-olefin.
 9. The ethylene/α-olefin interpolymer of claim1, wherein the ethylene/α-olefin interpolymer has a polydispersity indexfitting a Schultz-Flory distribution.
 10. The ethylene/α-olefininterpolymer of claim 1, wherein the ethylene/α-olefin interpolymer hasa formula (AB)n where n is at least 1, “A” represents a block ofpolymerized units in which ethylene is present in an amount greater than95 weight percent, and “B” represents a block of polymerized units inwhich α-olefin is present in an amount greater than 5 weight percentwherein each of block A and B has monomers randomly distributed withinthe block.
 11. The ethylene/α-olefin interpolymer of claim 1, whereinthe interpolymer is a block interpolymer comprising at least about 70mole percent ethylene.
 12. The ethylene/α-olefin interpolymer of claim1, wherein the interpolymer is a block interpolymer comprising at leastabout 80 mole percent ethylene.
 13. The ethylene/α-olefin interpolymerof claim 1 made using a shuttling agent selected from the groupconsisting of diethyl zinc, di(i-butyl)zinc, di(n-hexyl)zinc,triethylaluminum, trioctylaluminum, triethylgallium, i-butylaluminumbis(dimethyl(t-butyl)siloxane), i-butylaluminumbis(di(trimethylsilyl)amide), n-octylaluminum di(pyridine-2-methoxide),bis(n-octadecyl)i-butylaluminum, i-butylaluminum bis(di(n-pentyl)amide),n-octylaluminum bis(2,6-di-t-butylphenoxide, n-octylaluminumdi(ethyl(1-naphthyDamide), ethylaluminum bis(t-butyldimethylsiloxide),ethylaluminum di(bis(trimethylsilyl)amide), ethylaluminumbis(2,3,6,7-dibenzo-1-azacycloheptaneamide), n-octylaluminumbis(2,3,6,7-dibenzo-1-azacycloheptaneamide), n-octylaluminumbis(dimethyl(t-butyl)siloxide, ethylzinc(2,6-diphenylphenoxide), andethylzinc(t-butoxide).
 14. The ethylene/α-olefin interpolymer of claim1, wherein the α-olefin is 1-butene.
 15. The ethylene/α-olefininterpolymer of claim 1, wherein the α-olefin is 1-octene.
 16. Theethylene/α-olefin interpolymer of claim 1, wherein the M_(w)/M_(n) isfrom about 1.7 to about 3.5.
 17. The ethylene/α-olefin interpolymer ofclaim 1 wherein the interpolymer is characterized by having at least onefraction obtained by Temperature Rising Elution Fractionation (“TREF”),wherein the fraction has a block index greater than about 0.3 and up toabout 1.0.
 18. The ethylene/α-olefin interpolymer of claim 1 wherein theinterpolymer is characterized by having at least one fraction obtainedby TREF, wherein the fraction has a block index greater than about 0.1and up to about 0.4.
 19. The ethylene/α-olefin interpolymer of claim 10,wherein one or more “A” blocks comprise at least 98% of ethylene byweight.
 20. The ethylene/α-olefin interpolymer of claim 10, wherein oneor more “B” blocks comprise less than 50% of ethylene by weight.